Transformation of Monoterpenes and Monoterpenoids Using Gold-Based Heterogeneus Catalysts PDF

Brazilian Journal of Chemical Engineering (2020) 37:1–27
https://doi.org/10.1007/s43153-020-00013-1
REVIEW
Transformation of monoterpenes and monoterpenoids using

gold‑based heterogeneous catalysts
Jaime‑Andrés Becerra1 · Óscar Felipe Arbeláez2 · Aída‑Luz Villa1
Received: 29 May 2019 / Revised: 5 October 2019 / Accepted: 11 November 2019 / Published online: 5 February 2020
© Associação Brasileira de Engenharia Química 2020
Abstract
Gold is an attractive metal for using as catalyst because is very inert and resistant to air oxidation compared with other
metals; furthermore, when gold is dispersed as nanoparticles onto a support it attains exceptional catalytic properties in
organic reactions. Some heterogeneous gold catalysts have activity in the transformations of monoterpenes and monoterpe-
noids, natural organic compounds extracted from plants whose transformations produce substances with applications in fine
chemicals, pharmaceuticals, cosmetics, agriculture, polymers and food industries. This review describes the achievements of
some transformations of monoterpenes (α-pinene and limonene) and monoterpenoids (α-pinene epoxide, verbenol epoxide,
myrtenol, nopol, perillyl alcohol, geraniol, nerol, carveol, citronellol, isoborneol, borneol, menthol, isopulegol, citronellal,
carvone oxime and 2-adamantanol) reported from 2002 to 2018 through oxidation, hydrogenation, isomerization and amina-
tion over gold-based heterogeneous catalysts.
Keywords Gold · Monoterpenes · Heterogeneous catalysts · Oxidation · Isomerization · Hydrogenation · Amination
List of symbols met Methionine

BET Brunauer–Emmett–Teller MeCN Acetonitrile
C Activated carbon MPCHD (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)
cys Cysteine cyclohex-3-ene-1,2-diol
DMCPHP (2R)-2-[(1R)-2,2-dimethylcyclopent-3-en- MSU Michigan State University silica
1-yl]-2-hydroxypropanal n.r. Not reported
DMMBHD (2R,3R)-6,6-dimethyl-4-methylidenebicy- np Nanoparticles
clo[3.1.1]heptane-2,3-diol P Post-synthesis method
DP Deposition–precipitation method P Pressure
Ex Exfoliated PM Physical mixing
GNP Gold nanoparticles PVA Polyvinyl alcohol
HT Hydrotalcite rac Prepared with racemic amino acids ligands
HTMCPE 2-Hydroxy-1-[(1S)-2,2,3-trimethylcyclo- SBA Santa Barbara amorphous silica
pent-3-en-1-yl]ethanone Sproducts Products selectivity
IM Impregnation method T Temperature
M Metal t Time
MCM Mobil composition of matter silica TBHP Tert-butyl hydroperoxide
TEM Transmission electron microscopy
TOS Time-on-stream
* Aída‑Luz Villa UHP Urea hydrogen peroxide
aida.villa@udea.edu.co
WGSV Wet gas space velocity
1
Environmental Catalysis Research Group, Chemical Xsubstrate Substrate conversion
Engineering Department, Engineering Faculty, Universidad
de Antioquia UdeA, Calle 70 No. 52‑21, Medellín, Colombia
2
TERMOMEC, Facultad de Ingeniería, Universidad
Cooperativa de Colombia, Calle 50 No. 40‑74, Bloque A,
Piso 4, Medellín, Colombia
1 3 Vol.:(0123456789)
2 Brazilian Journal of Chemical Engineering (2020) 37:1–27
Introduction hydrosylation of allenes, hydrothiolation, (oxidative) ring

expansion, oxyarylation, rearrangements, cross-coupling
Gold is a natural and very popular precious metal that has and total synthesis reactions (Li et al. 2008; Shahzad et al.
been used since the past as a monetary system, jewelry and 2017). Gold species Au1+ and Au3+ are highly carbophilic
ornamentation due to its exclusivity and beauty (Vigneron as they are used for selective π-electrophilic activations
and Caps 2016). Although gold is a prized metal, it is more in organic compounds having C–C multiple bonds, Au3+
available and economical than other noble metals such as species are used in reductive elimination and the cation
Pt and Pd (Hutchings 2005). About 83% of mined gold is Au1+ in oxidative additions. Au/oxides have activity in the
used in jewelry and the rest for environmental applica- hydrogenation of unsaturated hydrocarbons and oxidation
tions, chemical processing, fuel cells and medicine, espe- of CO and hydrocarbons. Furthermore, gold complexes
cially in tumor diagnosis (van der Lingen 2005). Although have been used in the synthesis of arene-based pharmaceu-
the prices of heterogeneous catalysts are not mainly ruled ticals and agrochemicals (Echavarren et al. 2016; Shahzad
by the metal (Baddour et al. 2018), gold has long been et al. 2017).
ignored as a potential catalyst because of its surface resist- Terpenes are built up from isoprene units (C5H10) and are
ance to some chemicals and the added value. However, the largest group of natural products extracted from plants
most monetary systems are currently no longer backed for many different purposes in fine chemical, flavors, phar-
by gold and this is no longer the most expensive metal, maceutical and perfumes industries (Thomas and Bessière
giving way to others such as Rh, Pd and Pt. The huge min- 1989; Monteiro and Veloso 2004; Swift 2004; Degenhardt
ing exploitation, technified recycling and recovery have et al. 2009; Tracy et al. 2009). They comprise at least thirty
maintained gold price stability and boosted research for thousand compounds containing a wide variety of structural
industrial applications (Hashmi 2007). In consequence, types, such as monoterpenes C 10H20, sesquiterpenes C
15H30
gold has been used nowadays for many applications in and diterpenes C20H40 (Degenhardt et al. 2009). The selec-
electronics, biomedicine and optics because of its corro- tive transformation via microorganisms (Rozenbaum et al.
sion resistance, electrical conductivity and high ductility 2006; Marmulla and Harder 2014) or with catalysts is large
(Vigneron and Caps 2016). and difficult (Bogel-Łukasik et al. 2009) due to their high
The first gold catalysis was observed accidently in 1906 reactivity and the presence of carbon–carbon double bonds
during the oxidation of hydrogen on gold gauze and since with different functional groups. The uses of gold catalysts
then it had been studied for use as catalyst (Bone and for fine chemical synthesis are of interest because of their
Wheeler 1906). The oxidation of CO is one of the most activity in the transformations of complex organic com-
studied reactions over gold catalysts and reported as sensi- pounds. Nano-gold catalysis of organic reactions has been
tive to the nature of the support; for example, CO oxidation reviewed by several authors since the last decade (Hashmi
increases when alumina is doped with C eO2–FeOx mixed and Hutchings 2006; Corma and Garcia 2008; Stratakis and
oxides (Ramirez Reina et al. 2013). The major advantages Garcia 2012; Zhang et al. 2012; Simakova et al. 2013); how-
of nano-gold catalysts are their long time stability (Kresge ever, there is not a review focused only on monoterpenes
et al. 1992; Yang et al. 1998; Glaspell et al. 2008) and and monoterpenoids transformation. The objective of this
poison resistivity (Prati and Martra 1999). Catalytic activ- review is to describe the major achievements in the trans-
ity of gold has been directly related to the particle size formations of monoterpenes and monoterpenoids through
(Corma and Garcia 2008). Thus, when it is reduced in oxidation, hydrogenation, isomerization and amination using
size to the nanoscale the surface is not inert anymore and gold-based heterogeneous catalysts published from 2002 to
affords exceptional properties that currently have led to 2018. The information of these catalytic tests are the starting
the continuous growth and development of several gold- points required for selecting conditions that could be used on
based materials with catalytic activity in the fields of green a higher scale for pilot or industrial production of high value
chemistry, electrochemistry, environmental catalysis and added products that are useful in fine chemistry.
biology (Vigneron and Caps 2016; Shahzad et al. 2017).
Homogeneous and heterogeneous gold catalysts have been
used in the transformation of organic compounds under Oxidation
mild conditions through many different reactions such as
oxidation, hydrogenation, epoxidation, hydrochlorination, The oxidation of monoterpenes and partially oxidized
cyclization, cycloaddition, 1,4-conjugate addition, heter- monoterpenoids over heterogeneous catalysts is one of the
ocyclic (furan and benzofuran) synthesis, glycosylation, most common organic transformations of this subgroup of
hydroalkoxylation, hydroaminaloxylation, hydroamina- terpenes. It occurs because of two competitive pathways, one
tion, hydroarylation, hydroimination of terminal alkynes, due to the double bond epoxidation, for example the forma-
tion of α-pinene epoxide and limonene 1,2-epoxide from
13
Brazilian Journal of Chemical Engineering (2020) 37:1–27 3
their respective monoterpenes. In the second pathway, the gold-based heterogeneous catalysts, the size of the gold par-
oxidation through the replacement of an acid hydrogen with ticle and the nature of the support appear to be the most
an oxygen atom in the allylic position of the double bond important parameters with respect to the activity and selec-
produces allylic alcohols such as verbenol and carveol and tivity in the oxidation reactions not only of monoterpenes,
allylic ketones such as verbenone and carvone (see Fig. 1) but also of most organic compounds. Typically a low gold
as main products. The predominance of one pathway over content is necessary to obtain active and selective gold cata-
the other depends mainly on the type of catalyst, reaction lysts; a higher content would mostly promote the formation
conditions and oxidant influencing the reaction mechanism of large but inactive metal clusters (Martin et al. 2008).
and product selectivity. The transformation of monoterpe-
noids (mainly alcohols) occurs with less complexity than
the monoterpenes and leads to the formation of aldehydes,
ketones and carboxylic acids, Fig. 1. Epoxidation of double bonds and allylic
The oxidation over heterogeneous catalysts uses mainly oxidation
O2 (or air) and peroxides such as tert-butyl hydroperoxide
(TBHP), hydrogen peroxide and urea hydrogen peroxide Most research on monoterpene transformations has focused
(UHP) as oxidants. The peroxides have a strong influence on limonene and α-pinene because they can be produced on
in the formation of radicals in many reactions, and they are a large scale from waste of the citrus and paper industries,
often used as initiators when the oxidation is carried out respectively. Some of the reports about oxidation of these
with oxygen (Becerra and Villa 2019). In the reactions over hydrocarbons over gold heterogeneous catalysts towards
Camphor O
Isopulegone
Perillyl
aldehyde
OH
O
O
OH
OH OH
Neral Isoborneol Geranial
OH
Perillyl Isopulegol
alcohol
Nerol Geraniol
O OH Gold-based OH O
heterogeneous
Menthone Menthol
catalysts + [O] 2-adamantanol 2-adamantanone
O OH
O HO Limonene OH
-Pinene O
+ + Citronellol
Citronellal Citronellic acid

Carvone Carveol Limonene 1,2-epoxide
O
+ +
OH O
-Pinene epoxide Verbenol Verbenone
Fig. 1 Main monoterpenes and monoterpenoids oxidations over gold heterogeneous catalysts
13
4
Table 1 Heterogeneous gold-based catalytic systems used in monoterpenes and monoterpenoids epoxidation and allylic oxidation
13
Substrate (mmol) Oxidant (mmol) %Au, catalyst Catalyst Size of GNP, nm T (°C) t (h) Solvent (mL) Xsubstrate (%) Sproducts (%) References
mass,
mg
α-Pinene (10) H2O2 (30) 2.1%, Au/MCM-41 50 2.1 60 8 MeCN (5.0b) 73 α-Pinene epoxide (81), verbenol Yu et al. (2011)
(10), verbenone (4), others (5)
H2O2 (30) 2.0%, Au/MSU 50 4.7, > 20 60 8 MeCN (5.0 b) 62 α-Pinene epoxide (53), verbenol Yu et al. (2011)
H2O2 (30) 2.1%, Au/SBA-15 50 2.0 60 8 MeCN (5.0 b) 86 α-Pinene epoxide (79), verbenol Yu et al. (2011)
H2O2 (30) 1.4%, Au/SBA-15P 100 1.6 60 8 MeCN (5.0 b) 82 α-Pinene epoxide (95), verbenol Yu et al. (2011)
(2), verbenone (3)
α-Pinene (5) TBHP (5) AuCu/TiO2 100 3.8–3.9 70 24 MeCN (15) 97 α-Pinene epoxide (6.5), verbenol Ajaikumar et al. (2011)
(12.1), verbenone (47.9), others
(33.5)
TBHP (5) AuCo/TiO2 100 3.6 70 24 MeCN (15) 88 α-Pinene epoxide (6.3), verbenol Ajaikumar et al. (2011)
(52.3)
TBHP (5) AuRu/TiO2 100 1.5–10 70 24 MeCN (15) 73 α-Pinene epoxide (5.7), verbenol Ajaikumar et al. (2011)
(40.1)
TBHP (5) Au/TiO2 100 5.8 70 24 MeCN (15) 78 α-Pinene epoxide (4.6), verbenol Ajaikumar et al. (2011)
(53.3)
Limonene (1.6) Air, TBHP (0.08) HT-cys-Au n.r. n.r. 80 96 Toluene (15) 100 Limonene 1,2-epoxide (81), Leandro et al. (2018)
carvone (19)
Air, TBHP (0.08) HT-met-Au n.r. n.r. 80 96 Toluene (15) 100 Limonene 1,2-epoxide (69), Leandro et al. (2018)
carvone (31)
Ex
Air, TBHP (0.08) HT-cys-Au 10a n.r. 80 96 MeCN (5.0) 67 Limonene 1,2-epoxide (80), Leandro et al. (2018)
carvone (20)
Ex
Air, TBHP (0.08) HT-met-Au 10a 15-60 80 96 MeCN (5.0) 83 Limonene 1,2-epoxide (73), (Leandro et al. 2018)
carvone (27)
Air, TBHP (0.08) rac-HT-met-Au n.r. n.r. 80 96 Toluene (15) 100 Limonene 1,2-epoxide (75), Leandro et al. (2018)
carvone (25)
Air, TBHP (0.08) rac-ExHT-met-Au n.r. n.r. 80 96 Toluene (15) 89 Limonene 1,2-epoxide (79), Leandro et al. (2018)
carvone (21)
Xsubstrate substrate conversion, Sproducts products selectivity, MeCN acetonitrile, TBHP tert-butyl hydroperoxide, SBA-15P prepared by post-synthesis method, cys cysteine, met methionine, rac
prepared with racemic amino acids ligands, HT hydrotalcite, Ex exfoliated, GNP gold nanoparticles, n.r. not reported
a
Amount of exfoliated catalyst in mL
b
Amount of solvent in g
a specific set of oxygenated compounds are presented in formation of α-pinene epoxide followed the order Au/SBA-
Table 1. 15P > Au/SBA-15 > Au/MCM-41 > Au/MSU, with selectivi-
ties ranging from 53 to 95%; verbenol and verbenone were
Oxidation of α‑pinene the main by-products (Yu et al. 2011). A series of alloyed
bimetallic gold catalysts with Cu, Co and Ru supported on
α-Pinene is a monoterpene and one of the main constitu- TiO2 via the deposition–precipitation method were also used
ents of turpentine oil obtained from leaves, bark, and wood in α-pinene oxidation in a glass batch reactor, Table 1. TEM
of a wide variety of pines, that can be converted through images of the catalysts showed that the metallic nanoparti-
oxidation into more valuable compounds, such as epox- cles of 3–5 nm were finely distributed and dispersed on the
ides, alcohols, aldehydes and ketones (see Fig. 1) used in supports. The mean particle diameters of bimetallic catalysts
the production of flavors, insecticides and therapeutic drugs AuCu/TiO2 (3.8–3.9 nm), AuCo/TiO2 (3.6 nm) were slightly
(Suh et al. 2001; Becerra et al. 2016). The epoxides such as smaller than the monometallic species Au/TiO2 (5.8 nm),
α-pinene epoxide obtained from α-pinene are very impor- except for the bimetallic AuRu/TiO2 (1.5–10 nm) where the
tant intermediates and starting materials in the preparation metal nanoparticles presented agglomeration. As a result,
of more specific fine chemicals and pharmaceuticals (Lu larger particles were slightly less active for α-pinene conver-
et al. 2015). The allylic oxidation of α-pinene leads to the sion. However, in this study allylic oxidation and side reac-
production of α,β-unsaturated compounds such as verbenol, tions predominated over epoxidation. The major products
used in the preparation of fragrances and insecticides, and obtained (5.0 mmol substrate, 5.0 mmol TBHP 70%, ace-
verbenone that has applications in pharmaceuticals manufac- tonitrile, 70 °C, 24 h) were verbenone (25–48% selectivity),
turing, insecticides and food industry (Becerra et al. 2016). in addition to verbenol, α-pinene epoxide and alkyl-pinene
Yu et al. (2011) reported the activity of gold nanoparticles peroxide, which could be separated upon distillation. The
(GNPs) supported on ordered mesoporous organosilicas and most active and selective catalyst was AuCu/TiO2, affording
the evaluation in the epoxidation of different olefins such as 4 cycles of constant catalytic activity with 3% deactivation
α-pinene in a batch reactor, Table 1. The catalytic materials based on fresh substrate conversion to the last catalyst cycle.
Au/MCM-41, Au/MSU and Au/SBA-15 were prepared by The temperature, nature of the catalysts and the choice of
the one-pot method, whereas the Au/SBA-15P material was solvents greatly influenced the reaction rate. The combined
synthesized using the post-synthesis method. TEM images free radical and heterogeneous reaction mechanism proposed
of the materials indicated that all gold-based catalysts sup- involves chemical adsorption of TBHP at the perimeter
ported onto the organosilicas MCM-41, MSU and SBA-15 interface between the metal particles and the T iO2 to pro-
had dispersed gold nanoparticles. The pore structure system duce alkoxy and alkyl-peroxy adsorbed radicals. The radical
of Au-MSU was found to be worm-like, Au-/MCM-41 sam- active sites react with α-pinene, resulting in the formation of
ples showed unexpected highly curved and tortuous pore allyl and alkyl-pinene peroxy radical intermediates and the
structures; whereas Au-SBA-15 materials presented the typi- different reaction products (Ajaikumar et al. 2011).
cal uniform hexagonal arrays of cylindrical mesopores. The
preparation method, as well as the pore architectures of the Oxidation of limonene
materials, played crucial roles in the particle size, disper-
sion of the GNPs and catalytic performance. For example, Limonene is the main component of the essential oils
materials with 1-D pore structure and prepared by the post- extracted from citrus fruit peels such as sweet oranges, tan-
synthesis method (Au/SBA-15P) dispersed GNPs better and gerines, lemons and grapefruits in a concentration around
showed better catalytic activity than the 3-D pore structure 72–96 wt.%. Although limonene has several direct industrial
Au/MSU prepared by the one-pot method. However, the cat- applications, it also has been extensively used as precursor
alytic activity of Au/SBA-15P remained constant 2 cycles material in the synthesis of a variety of chemicals, including
less than the materials prepared by the one-pot method. a set of oxygenated compounds (epoxides, ketones, alcohols,
Mean particle sizes of Au/MSU (4.7 nm and > 20 nm) were aldehydes and acids) for the production of fine chemicals
higher than those of the materials Au/SBA-15 (2.0 nm), Au/ with important applications in some industries (Lima et al.
SBA-15P (1.6 nm) and Au/MCM-41 (2.1 nm); as a con- 2006; Becerra and Villa 2019). Limonene 1,2-epoxide is
sequence, they presented better catalytic activity. α-Pinene a fine chemical monoterpenoid with potent antinocicep-
conversions between 62 and 86% were obtained with an tive and antitumoral activity prepared from limonene, and
excess of H2O2 as oxidant (10 mmol substrate, H2O2/sub- widely used as a building block in the synthesis of chemi-
strate = 3 (mol/mol), 8 cycles of constant catalytic activity cals, pharmaceutical products, perfumes, cosmetics, food
in both α-pinene conversion and α-pinene epoxide selectiv- additives, insecticides and polymers (de Almeida et al. 2012;
ity), polar solvent acetonitrile, under basic conditions at pH Charbonneau et al. 2018). It is the most common epoxide
9.0–9.5, 60 °C, 8 h. The activity of the catalysts towards the synthesized with high yields from limonene oxidation
13
using heterogeneous catalyst based on different metals and could poison some catalysts (Costa et al. 2012). Gold het-
TBHP, O2 or H 2O2 as oxidants (Becerra and Villa 2019). erogeneous catalysts used in the monoterpenoid (most of
Recently (Leandro et al. 2018) immobilized gold nano- them alcohols) oxidation listed in Table 2 focused mainly
particles immobilized over Mg/Al hydrotalcite clay (HT) on the transformation of geraniol and its isomer nerol, cit-
containing cysteine (cys) and methionine (met) amino ronellol, carveol, perillyl alcohol, borneol, menthol and
acids in both bulk and exfoliated (Ex) forms, Table 1. The 2-adamantanol.
morphology and dimensions of the exfoliated nanosheets
were also examined by TEM. The images showed the pres- Oxidation of geraniol and nerol
ence of agglomerates of gold nanoparticles in several sizes
(15–60 nm) and shapes (spherical, hexagonal, triangle or Geraniol is a monoterpenoid alcohol found in rose, gera-
rod) in the exfoliated catalyst ExHT-met-Au. The images also nium, palmarosa and citronella oils used in fragrances and
show that the exfoliated clay is present as very thin sheets of flavoring, the food industry, as an antimicrobial, antioxidant,
homogeneous contrasts. The Au nanoparticle catalysts pre- mosquito repellent and in the biosynthesis of other terpenes
pared by a biomimetic method were successfully used in the (Sell 2003; Yue et al. 2017). Nerol, the isomer of geraniol,
aerobic epoxidation of several olefins including limonene; on the other hand is less widespread, but also found in rose
at 24 h the limonene conversion was around 15–42% and and palmarose oils and used in fragrances and household
at 96 h, limonene conversion was 67–100% with 69–81% products (Sell 2003; Lapczynski et al. 2008b). The cata-
limonene 1,2-epoxide selectivity. The reactions were car- lytic oxidation of geraniol and nerol produces the racemic
ried out using air as oxidizing agent and TBHP as initia- aldehyde citral; the E-isomer of citral, also called citral A,
tor, 1.6 mmol substrate, 0.08 mmol initiator TBHP/decane, corresponds to geranial with an intense lemon (citrus) odor.
1 mol% catalyst, solvent acetonitrile or toluene, 80 °C and The Z-isomer of citral is known as citral B or neral with
96 h. The exfoliated forms used 10 mL of exfoliated cata- less intense lemon odor than geranial (Sell 2003). Each ste-
lyst (0.016 mol Au). The exfoliated catalysts ExHT-cys-Au reospecific aldehyde can be obtained from their precursor
and ExHT-met-Au yielded higher product stereoselectivity (geraniol or nerol), but the stereoselectivity depends mainly
in the case of limonene epoxidation obtaining only the cis on the catalyst and the reaction conditions. Geranial and
configuration, whereas non-exfoliated achieved 63–67% cis neral also have applications in perfumery, medicine, food
configuration of limonene 1,2-epoxide. The reaction mecha- and synthesis of vitamins such as vitamin A via ionones
nism considered was based mainly on the data collected for (Bastiani et al. 2004; Liao et al. 2015). Haider and Baiker
cis-cyclooctene epoxidation. The reaction follows a radical (2007) reported gold nanoparticles containing Cu, Mg and
pathway in which TBHP, used in low amount, acts as initia- Al on mixed oxides as catalysts in the aerobic liquid-phase
tor of the reaction, decomposes at the surface of gold nano- oxidation of different alcohols such as geraniol and citron-
particles into t-BuO* or t-BuOO* species, whereas oxygen ellol with high selectivity, Table 2. The materials were pre-
provided in atmospheric air assists the oxidation process. pared by flame spray pyrolysis and the TEM images showed
TBHP-derived radicals abstract hydrogen from the substrate, that the support (mostly amorphous and with some crys-
producing allylic radicals whose interaction with O 2 gives talline regions) exhibited particle size distributions with
raise an intermediate alkyl hydroperoxide radicals, which agglomerated primary sizes in the 10–15 nm range, onto
are the precursors of epoxides and some by-products (mainly which 6-9 nm gold particles (mostly spherical and minor
allylic ketones and alcohols) after further propagation and with some irregular shapes) were deposited by means of
termination steps (Leandro et al. 2018). deposition–precipitation. The catalytic activity depends
strongly on the composition of the support, with Cu and
Oxidation of alcohols, aldehydes and ketones Mg playing crucial roles as promoters. The best performance
was achieved for a ternary mixed-oxide-supported gold
The oxidations of alcohols and aldehydes into ketones and catalyst with the composition Au/Cu5Mg1Al2Ox. Geraniol
carboxylic acids are some of the most challenging reactions was converted to geranial with 99% selectivity and TOF
in synthetic organic chemistry for the production of a wide of 53 h−1; whereas, citronellol was transformed with lower
range of products with many applications in different fields yield (Haider and Baiker 2007).
of the chemical industry, Fig. 1; using conventional oxidiz- Supported gold nanocrystals prepared by coprecipita-
ing agents likely to be replaced such as permanganate, nitric tion, deposition-precipitation and impregnation methods
acid and chromium oxides (Martin et al. 2008). Although have been investigated for the oxidation of geraniol (under
the oxidation of alcohols over gold catalysts can be carried solvent-free conditions in the absence of base) using SiO2,
out under base-free conditions, it often requires a base to CeO2, Fe2O3, activated carbon C and TiO2 as supports in
promote the abstraction of hydrogen from the substrate and a batch autoclave reactor (40 mL substrate, 1500 rpm),
to capture free carboxylic acid formed in the reaction, which Table 2. Geraniol was 2–47% converted to both citral
13
Table 2 Heterogeneous gold-based catalytic systems used in alcohol, aldehyde and ketone-based monoterpenoid oxidation
Substrate (mmol) Oxidant %Au, catalyst Catalyst mass, mg Size of GNP, nm T (°C) P (bar) t (h) Solvent (mL) Xsubstrate (%) Sproducts (%) References
Geraniold O2 Au/Cu5Mg1Al2Ox 50 6–9 90 50b 2 Mesitylene (2.0) 94 Geranial (99), oth- Haider and Baiker
ers (1) (2007)
O2 Au/SiO2 200 n.r 100 2 3 None 0.21 Geranial (30.5), Enache et al. (2005)
neral (58.2),
nerol (5.9), others
(5.4)
O2 Au/SiO2 200 n.r 100 6 3 None 2.1 Geranial (23), Enache et al. (2005)
nerol (6.4), others
(70.6)
Geraniol (40a) O2 Au/CeO2 200 n.r 100 2 3 None 46.7 Geranial (4.8), Enache et al. (2005)
neral (23.8),
nerol (2.3), others
(69.1)
Au/C 200 n.r 100 2 3 None 17.5 Geranial (12.1), Enache et al. (2005)
O2
neral (65.3),
nerol (6.2), others
(16.4)
O2 Au/TiO2 200 n.r 100 2 3 None 11.6 Geranial (18.6), Enache et al. (2005)
neral (48.1),
nerol (8.0), others
(25.3)
O2 Au/Fe2O3 200 n.r 100 2 3 None 12.6 Geranial (11.2), Enache et al. (2005)
neral (66.9),
nerol (6.0), others
(15.9)
Nerol (0.4) O2 2.6%, Au/MgO 10 3.4 80 10.13 8 Methanol (2.0) 50 Neral (90), others Costa et al. (2012)
(10)
O2 2.6%, Au/MgO 10 3.4 80 10.13 8 Toluene (2.0) 25 Neral (85), others Costa et al. (2012)
(15)
Citronellole O2 Au/Cu5Mg1Al2Ox 50 6–9 90 50b 2 Mesitylene (2.0) 37 Citronellal (98) Haider and Baiker
others (2) (2007)
Citronellol (0.4) O2 2.6%, Au/MgO 20 3.4 120 10.13 8 Methanol (2.0) 20 Citronellal (46), Costa et al. (2012)
others (54)
Citronellal (500) O2 1%, Au/Al2O3 10800 1–5 80 1.013 4 H2O (269) 100 Citronellic acid Martin et al. (2008)
(NaOH) (92), others (8)
Citronellal (50) O2 1%, Au/Al2O3 1000 1–5 80 1.013 5 H2O (400) 100 Citronellic acid Martin et al. (2008)
13
(urea) (84), others (16)
Citronellal (50) O2 1%, Au/TiO2 (urea) 1000 1–5 80 1.013 5 H2O (400) 100 Citronellic acid Martin et al. (2008)
(48.4), others
(51.6)
Carveol (0.4) O2 2.6%, Au/MgO 20 3.4 120 10.13 8 Methanol (2.0) 86 Carvone (100) Costa et al. (2012)
7
8
Table 2 (continued)
Substrate (mmol) Oxidant %Au, catalyst Catalyst mass, mg Size of GNP, nm T (°C) P (bar) t (h) Solvent (mL) Xsubstrate (%) Sproducts (%) References
13
Carveol (0.4) O2 2.6%, Au/MgO 20 3.4 120 10.13 8 Toluene (2.0) 76 Carvone (100) Costa et al. (2012)
trans-Carveol (1.0) Air 0.45%, Au/npCeO2 n.r. 4.4-9.2 90 1.013 20 Toluene (5.0) 88 Carvone (99), oth- Abad et al. (2008)
ers (1)
trans-Carveol O2 npAu/npCeO2 n.r. 4 120 1.013, 35b 21 None 91 Carvone (98), oth- Abad et al. (2007)
(12.5) ers (2)
trans-Carveol Air Au–Pd/TiO2 n.r. n.r. 120 1 None 79 Carvone (47), oth- Abad et al. (2006)
ers (53)
Isoborneol (1.2) O2 2.6%, Au/MgO 40 3.4 110 10.13 10 Methanol (2.0) 98 Camphor (100) Costa et al. (2012)
(−)-Borneol (1.0) Air 1.8%, Au/npCeO2 n.r. n.r. 90 1.013 24 Toluene (5.0) 91 Camphor (98), oth- Abad et al. (2008)
ers (2)
Perillyl alcohol O2 2.6%, Au/MgO 20 3.4 110 10.13 7 Methanol (2.0) 90 Perillyl aldehyde Costa et al. (2012)
(1.2) (97), others (3)
Menthol (0.4) O2 2.6%, Au/MgO 10 3.4 130 10.13 8 Methanol (2.0) 12 Menthone (100) Costa et al. (2012)
Isopulegol (0.4) O2 2.6%, Au/MgO 20 3.4 120 10.13 8 Methanol (2.0) 34 Isopulegone (80), Costa et al. (2012)
others (20)
2-Adamantanol Air 1.8%, Au/npCeO2 n.r. 4.4–9.2 90 1.013 2 Toluene (5.0) >99 2-Adamantanone Abad et al. (2008)
(1.0) (> 99), others
(< 1)
Air Au/HT 100 n.r. 40 1.013 8 Toluene (5.0) 95 2-Adamantanone Mitsudome et al.
(99), others (1) (2009)
Xsubstrate substrate monoterpenoid conversion, Sproducts product selectivity, C activated carbon, np nanoparticles, HT hydrotalcite, n.r. not reported
a
Amount in mL
b
Flow rate in mL min−1
c
Flow rate in normal N mL m
in−1
d
Molar ratio substrate/Au = 113
e
Molar ratio substrate/Au = 152
configurational isomers; however, in most of the cases reac- 92% selectivity was achieved over Au/Al2O3 (NaOH) with
tions were more selective for neral (around 24–67%) and total conversion of citronellal at pH 12 and a temperature
Au/CeO2 material presented 0.05% Au leaching (Enache of 80 °C and no significant gold leaching appeared to occur
et al. 2005). The liquid-phase oxidation of nerol and a wide during tests (Martin et al. 2008).
range of monoterpenic alcohols (isoborneol, perillyl alco-
hol, carveol, citronellol and menthol) was also studied by Oxidation of carveol and perillyl alcohol
Costa et al. (2012) over gold nanoparticles supported on
magnesium oxide using molecular oxygen in the absence of Carveol and perillyl alcohol are monoterpenoids that can be
co-catalysts or additives, Table 2. Au/MgO prepared through obtained from the allylic oxidation of limonene. Carveol is
the deposition–precipitation method was able to convert found in peppermint and cumin oils, used in fragrances, cos-
25–50% nerol into neral with 85–90% selectivity in a stain- metics, food industry, medicine and organic synthesis (Bha-
less steel batch reactor (10 atm of O2, solvent methanol (or tia et al. 2008c). Perillyl alcohol occurs in cherries, lavender,
toluene), 10 mg catalyst 2.6 wt.% Au, 80 °C, 8 h). TEM spearmint, lemongrass, sage and peppermint oils; it shows
micrographs show metallic gold nanoparticles of hexagonal potent anticancer activity and is used as an ingredient in
shape with a mean diameter of 2.3 nm for the fresh catalyst. cleaning and cosmetics products (Liston et al. 2003; Alonso-
After sample treatment at high temperature (up to 350 °C) Gutierrez et al. 2013). The oxidation of carveol produces
the nanoparticles agglomerate with a size from 1 to 9 nm and carvone (see Fig. 1), a fine chemical component of Men-
a mean of 3.4 nm (Costa et al. 2012). tha spicata L. (spearmint) and caraway oils, widely used as
additive in pharmaceuticals, flavoring, chewing gums, oral
Oxidation of citronellol and citronellal hygiene products, food, beverage, fungicides, insecticides
and antibacterial agents (de Carvalho and da Fonseca 2006).
Citronellol that usually occurs in rose and geranium oils Perillyl alcohol can further be oxidized to perillyl aldehyde
is another monoterpenoid used in fragrances, cosmetics and perillic acid, Fig. 1.
and household products that can be converted by oxidation The liquid-phase oxidation of carveol studied by Costa
into citronellal, a very effective insect repellent present in et al. (2012) in a stainless steel batch reactor and over Au/
Eucalyptus oil (Sell 2003; Lapczynski et al. 2008a). Both MgO produces only carvone after 76–86% carveol conver-
monoterpenoids are precursor of citronellic acid or calli- sion (10 atm of O 2, methanol or toluene as solvent, 20 mg
trol, a β-methyl branched acid and major component of the catalyst 2.6 wt.% Au, 120 °C, 8 h). Under similar condi-
essential oils of Pelargonium vitifolium (L.) L’Hérit. (Gera- tions 90% perillyl alcohol was transformed into perillyl
niaceae) and Pelargonium papilionaceum (L.) L’Herit in aldehyde with 97% selectivity over Au/MgO catalyst. Abad
a concentration of 77–89% (Demarne and Van der Walt et al. (2006) reported that gold nanoparticles supported on
1992; Lis-Balchin and Roth 1999), used as preserving agent ceria were excellent heterogeneous catalysts for the aerobic
because of its antimicrobial effect (Martin et al. 2008). The oxidations of monoterpenoid alcohols such as trans-carveol,
ternary mixed-oxide-supported gold Au/Cu 5Mg 1Al 2O x (−)-borneol and 2-adamantanol. TEM analysis of the Au/
catalyst gave 32% citronellol conversion towards citronellal CeO2 catalyst showed that the gold nanoparticles were not
with 97% selectivity (50 mL min−1 O2, solvent mesitylene, agglomerated on the support and had sizes from 1 to 15 nm
90 °C, 2 h) (Haider and Baiker 2007). The Au/MgO catalyst and with a mean diameter of approximately 4 nm. The cat-
reported by Costa et al. (2012) showed around 20% of citron- alytic activity correlates linearly with the total number of
ellol conversion with 54% selectivity to citronellal (stainless external gold atoms and with the surface coverage of the
steel batch reactor, 10 atm of O2, solvent methanol, 20 mg support. Carvone was the main oxidation product obtained
catalyst 2.6 wt.% Au, 120 °C and 8 h). The oxidation of with 98–99% selectivity from 88 to 91% carveol conversion
citronellal to citronellic acid was studied under aqueous con- over Au/CeO2, (air or O 2, 90–120 °C, 20–21 h), Table 2.
ditions using molecular oxygen as oxidant in a glass auto- Toluene was the most suitable solvent for the transforma-
clave batch reactor with gold nanoparticles supported on tions; however, the reaction also occurs solventless with
alumina and titania, Table 2. The catalysts were synthesized high selectivity. The catalytic activity of the material was
by the deposition–precipitation method using urea or NaOH. kept constant for 5 cycles (in benzyl alcohol oxidation) if
TEM images showed that for both fresh and spent catalysts, washed with NaOH with slight leaching of gold only dur-
the gold particles were dispersed on all the supports with ing the washing process (not during the reaction); other-
sizes ranging from 1 to 5 nm. The reactions were carried wise, strong deactivation was observed if the material is not
out at 60–90 °C, with 200 NmL m in−1 O2, pH values from washed. A reaction mechanism proposal that explains all
9 to 12 because radical-initiated reactions lead to undesired experimental results consists of the formation of metal–alco-
by-products, especially at pH < 9. Citronellic acid can be holate, β-hydride shift from carbon to metal and M–H oxida-
obtained with higher yield using alumina as support; around tion (Abad et al. 2007, 2008). Gold(core)–palladium(shell)
13

nanoparticles supported on titania Au–Pd/TiO2 was more Jurgen Arpe 2003). Selective hydrogenation of terpenes
active than Au/CeO2 materials in aerobic carveol oxidation; produces valuable building blocks for chemicals used in
selectivity to carvone was around 47% (Abad et al. 2006). pharmaceuticals, agrochemical and perfume industries
(Meylemans et al. 2012). The catalysts generally used for
Oxidation of isoborneol, borneol, menthol, isopulegol hydrogenation are nanoparticles of Pd, Ni, Ru, or Pt (Che
and 2‑adamantanol and Bennett 1989). Initially gold catalysts were known for
selective and preferential oxidation reactions, but they are
Isoborneol and (−)-borneol are isomers and components of also highly effective for selective hydrogenation (Hutch-
many essential oils used in medicine, as natural insect repel- ings 2008). Gold was used as catalyst for hydrogenation by
lent, and in the production of camphor (Sell 2003; Bhatia (Yolles et al. 1971; Bond et al. 1973) in alkyne hydrogena-
et al. 2008a, b). Menthol is an organic compound made syn- tion reactions and it was reported that low loadings of Au
thetically or obtained from the oils of cornmint and pepper- on Al2O3 and on SiO2 were active in alkene hydrogenation;
mint with numerous uses in medicine, oral hygiene products, the activity was attributed to Au particles < 4 nm in size
food, perfumery and chemical synthesis. The oxidation of (Bond and Sermon 1973).
menthol produces menthone (see Fig. 1) that occurs natu- Several reviews on gold as a hydrogenation catalyst
rally in a number of essential oils and is also used in flavor- were reported by Nikolaev et al. (2009), Kartusch and
ing, perfume and cosmetics for its characteristic minty odor van Bokhoven (2009) and Gluhoi et al. (2010). The use
(Sell 2003). Isopulegol is a monoterpenoid that has been of gold catalysts in chemoselective hydrogenation of α,β-
found in the essential oils of several aromatic plants, includ- unsaturated aldehydes and selective partial hydrogenation
ing Cannabis, with diverse biological activities, converted of lower hydrocarbons (C2–C6) was reported by McEwan
by oxidation to isopulegone (Silva et al. 2012). et al. (2010). The development of gold catalysts for use in
The 2-adamantanol is a chemical compound used in the hydrogenation reactions was reviewed by Cárdenas-Lizana
preparation of 2-adamantanone, both are derived from ada- and Keane (2013). Experimental hydrogenation data and
mantane considered as a synthetic monoterpene belonging theoretical calculations on a well-structured gold surface
to the diamondoid family. Adamantane-derivatives usually for getting details of reaction mechanism was reported by
have practical application in drugs, polymeric materials, and Pan et al. (2013). Supported monometallic gold catalysts for
thermally stable lubricants (Steeghs et al. 2007; Elangovan selective liquid phase hydrogenation reactions were studied
et al. 2008). Au/MgO and Au/npCeO2 proved to be excel- by Hari and Yaakob (2015). Supported gold catalysts have
lent catalysts in camphor production from isoborneol and in shown activity in chemoselective hydrogenations (Mohr
(−)-borneol aerobic oxidation, respectively, using a batch and Claus 2001; Haruta 2003; Boronat et al. 2007; McEwan
reactor, with 98–100% selectivity (Abad et al. 2008; Costa et al. 2010). Au supported on ZnO favors mainly the for-
et al. 2012). Menthol and isopulegol were also highly selec- mation of single crystalline particles where its morphology
tive to menthone and isopulegone over Au/MgO catalyst can affect the chemoselectivity (Mohr et al. 2003a; Mohr
(see Table 2), but the conversion around 12–34% was quite et al. 2003b). Moreover, nanoparticles of gold supported on
low (Costa et al. 2012). Au/npCeO2 and hydrotalcite-sup- oxides could be particularly active for hydrogenation reac-
ported gold nanoparticles Au/HT were found to be highly tions (Bailie et al. 2001; Milone et al. 2007). It has been
efficient heterogeneous catalysts for the aerobic oxidation of reported that nanocrystalline fine powders of ZnO are ade-
2-adamantanol to 2-adamantanone in a batch flask reactor quate for gold deposition, because of the presence of acidic
(Mitsudome et al. 2009; Costa et al. 2012). Au/HT can be (Zn2+) and basic ( O2−) surface sites, as well as exposed
used up to 4 cycles in cyclohexanol oxidation without any crystal faces and structures, and the possibility of electron
significant loss in activity and selectivity, with around 1% of transfer between the adsorbent and the adsorbate (Thomp-
deactivation based on fresh substrate conversion to the last son 1999; Bailie et al. 2001; Krishna et al. 2010). Gold has
catalyst cycle (Mitsudome et al. 2009). less ability to chemisorb hydrogen compared to other met-
als such as Pt and Pd (Fu et al. 2011; Pattamakomsan et al.
2011; Primo et al. 2011; Qi et al. 2011). Using unsintered
Hydrogenation thin gold film, hydrogen reacts with low coordinate gold
atoms on edge sites and corner sites (Stobiński et al. 1999).
Catalytic hydrogenation is one of the most important reac- Reversible and weak adsorption of hydrogen was suggested
tions that is widely used in industry. The main problem on titania supported nano-gold (Lin and Vannice 1991) and
with catalytic hydrogenation reactions is their chemical Au/Al2O3 (Bus et al. 2005). Boronat et al. (2009) concluded
and stereo-selectivity (Ponec 1997). The selective hetero- that, for hydrogen dissociation over Au/TiO2, the active gold
geneous hydrogenation plays a vital role in the production sites are small gold particles with a higher fraction of low
of fine chemicals on a multi-ton scale (Weissermel and coordinated gold atoms occupying edges and corners.
13
The selective hydrogenation of carbonyl groups in α,β- depends on the selective hydrogenation of one of the three
unsaturated aldehydes to form unsaturated alcohols is desir- groups that can be hydrogenated. The unsaturated alcohols,
able because they are important intermediates for several nerol and geraniol, are obtained from hydrogenation of the
industrial applications (Gallezot and Richard 1998; Castille- carbonyl group; citronellal and its derivatives, isopulegol
jos et al. 2012). This chemoselective hydrogenation is not and menthol are obtained from hydrogenation of the conju-
thermodynamically favored (Claus 2005) and, for kinetic gated double bond. 3,7-Dimethyloctanol and 3,7-dimethyl-
reasons, the C=C bond is more reactive than the C = O group octanal are the products from hydrogenation of the isolated
(Demidova et al. 2015). Supported gold catalysts are good C=C (Corma et al. 2007). The hydrogenation of citral to
for the selective hydrogenation of α, β unsaturated aldehydes form 3,7-dimethyl-2,6-octadien-1-ols (geraniol and nerol)
to corresponding α, β unsaturated alcohols (Liu et al. 2010), is desirable because of the use of these alcohols in the food,
in contrast to hydrogenation with conventional hydrogena- pharmaceutical and cosmetic industries (Aprile et al. 2009).
tion catalysts that give saturated alcohols and aldehydes Au/Fe2O3 (Table 3) produces nerol plus geraniol with a
(Hari and Yaakob 2015). Supported nanostructured gold selectivity > 95% and is better than using Pt/Fe2O3 owing to
catalysts show high selectivity towards hydrogenation of preferential adsorption of the molecule on gold through the
C=O bonds in the presence of C=C double bonds dur- carbonyl group (Milone et al. 2002). A loss of 20% in activ-
ing the conversion of unsaturated aldehydes or ketones to ity of the catalysts was observed after recycling, but with no
unsaturated alcohols (Schimpf et al. 2002; Claus et al. 2004; changes in product distribution.
Khanderi et al. 2010). Stereoselective hydrogenation of the C=O bond in citral
hydrogenation to nerol by Au/Al2O3-PVA prepared by wet
Hydrogenation of citral impregnation in the presence of sodium citrate and polyvinyl
alcohol (PVA) was reported by Caballero et al. (2010). BET
Hydrogenation of citral (3,7-dimethyl-2,6-octadienal), analysis showed that the textural properties of the support
Fig. 2, can give several products that are used in flavors, did not change with the presence of PVA or gold; the size
pharmaceuticals, and cosmetics; the product obtained of the gold particles detected by TEM was about 10–30 nm
+ +
Menth-3-en Menth-2-en Menth-1-en
N OH
OH
Geraniol + Nerol
Carvone oxime (-)-Limonene
O O O
O
+
Gold-based O O
heterogeneous
cis/trans-
Carvomenthone
cis/trans-
Dihydrocarvone
Carvone catalysts + [H]
Citral 3,7-Dimethyl Dihydrocitronellal
octenal
OH
O
(-)-Carveol
OH OH O OH OH
Carvotanacetone Menthol Isopulegol Citronellal Citronellol 3,7-Dimethyl

octanol
Fig. 2 Main monoterpenes and monoterpenoid hydrogenation over gold heterogeneous catalysts
13

12
Table 3 Heterogeneous gold-based catalytic systems used in monoterpene and monoterpenoid hydrogenation

Substrate (mmol) %Au wt., catalyst Catalyst mass, mg Size of GNP, nm T (°C) PH2 (bar) t (h) Solvent (mL) Xsubstrate (%) Sproducts (%) References
13
Citral (3) 3.1, Au/Fe2O3 n.r. n.r. 60 atmospheric, H2 n.r. Ethanol (25) 90 Geraniol + nerol Milone et al. (2002)
flow (95%), citronellol
(2.84), citronellal
(0.18)
Citral (5) 0.01, Au/Al2O3- 200 10–30 90 6.2 7 Hexane (50) 48 Nerol (98), geraniol Caballero et al.
PVA (1) (2010)
Citral (2) 1.8, Au(0)/TiO2 16.7 2-4 80 40, 80 (CO2) 4 None 8 Dihydrocitronellal Liu et al. (2010)
(5), citronellal
(67), isopulegol
(3), geran-
iol + nerol (26)
Citral (2) Pd(2)/Au(0)/TiOb,c
2 16.7 4-7 80 40, 80 (CO2) 0.5 None 43 Dihydrocitronellal Liu et al. (2010)
(10), citronellal
(61), isopulegol
(25), others (5)a
Citral (2) Pd(2)/TiO2 + Au(0)/ 16.7 + 16.7 2-4 80 40, 80 (CO2) 0.5 None 85 Dihydrocitronellal Liu et al. (2010)
TiOb,d
2 (14), citronellal
(80), isopulegol
(3), others (3)a
Citral (12) 2, Au/MgxAlO 500 3.6 120 9.29 2 Ethanol (78) 56.4 Geraniol + nerol You et al. (2009)
(97.5), saturated
aldehyde (1.2),
saturated alcohol
(1.3)
Limonene (10) 1.9, Au/TiO2 336 1.9 ± 1.0 100 9 21 Methanol (36) 14 Terpinolene (40), Demidova et al.
α-terpinene (10), (2015)
γ-terpinene (8);
menth-1-en (26),
menth-3-en (9),
menth-2-en (7)
Carvone (10) 1.9, Au/TiO2 336 1.9 ± 1.0 100 9 13 Methanol (36) 90 Dihydrocarvone (62, Demidova et al.
trans/cis = 1.8), (2015)
carvomenthone
(15), others (23)
Carvone oxime (5) 1.9, Au/TiO2 140 1.9 100 9 23 Methanol (15) 22 Carvone (15), dihy- Demidova et al.
drocarvone (80), (2016)
trans/cis = 4.0)
and were inside the support matrix. When the catalyst was
calcined at 300 °C with PVA, 48% conversion of citral and
Authors explained that Au(0) and Pd(0) are reduced samples and Pd(2) is not reduced. However, it does not indicate all metal species exist in the zero-valent or di-valent state in the samples
Dihydrocarvone (30, Demidova et al. 99% nerol selectivity were obtained for an Au loading of
0.01% and the selectivity was related to the stabilizing effect
References
of PVA.
(2015)
Liquid-phase reduction of α,β-unsaturated aldehydes to

the corresponding α,β-unsaturated alcohols was investi-
gated on gold catalysts supported on MgxAlO hydrotalcite
thone (12), others
carvotanacetone
(30), carvomen-
trans/cis = 1.5),
(x = Mg/Al molar ratio) calcined at various temperatures

(100–500 °C) prior to the reactions (You et al. 2009). TEM
Xsubstrate (%) Sproducts (%)
analysis showed that no significant agglomeration of gold

(28)
particles occurried when the calcination temperatures were

below 400 °C. During the hydrogenation of citral over Au/
MgxAlO hydrotalcite, the authors observed that the activity
of the catalyst increased with temperature due to weakening
of the C=C bond interaction with nano-gold. Over 2% Au/
Methanol (36) 18
Mg2AlO (120 °C, 929 kPa), citral conversion was 56.4% and

t (h) Solvent (mL)
selectivity to unsaturated alcohol was 97.5%.

The selective hydrogenation of citral was studied in
supercritical CO2 with various TiO2-supported monometal-
lic and bimetallic Pd and Au catalysts (Liu et al. 2010). For
unreacted Pd(2)/TiO2 samples, it was difficult to differentiate
21
the particles in TEM analysis, probably due to high disper-

sion of the Pd precursors. The Au particle size of reduced
Au(0)/TiO2 was 3.5 nm. The particle size of Pd(2)/Au(0)/
TiO2 was around 5 nm; after reduction, bimetallic particles
Catalyst mass, mg Size of GNP, nm T (°C) PH2 (bar)
of about 12 nm were formed. The HRTEM analysis of those

large particles suggested the formation of a Pd–Au alloy.
Au/TiO2 systems were less active for citral hydrogenation
9
(Liu et al. 2010).

100
Hydrogenation of limonene
Limonene hydrogenation over Au/TiO2 in Table 3 (10 mmol

1.9 ± 1.0
substrate, 36 mL solvent, 336 mg of Au/TiO2, 0.3 mol% Au

to substrate, 100 °C, 9 bar of H2 atmosphere, 21 h) gave
Geraniol, nerol, citronellol, 3,7-dimethyloctanol, and menthol
a conversion of 14% (Demidova et al. 2015). Combined

selectivity of 58% to the isomers terpinolene, α-terpinene,
γ-terpinene was obtained, Fig. 3. The hydrogenation prod-
ucts, Fig. 2, included menth-1-ene with 26% selectivity
(Demidova et al. 2015).
336
Hydrogenation of carvone
%Au wt., catalyst
Pd(2)/TiO2 contains 0.08% Pd wt.

1.9, Au/TiO2
Carvone is a widespread natural monoterpenoid (Macaev

1.9% Au wt. and 0.13%Pd wt.
2013) that is used in food and perfumery industry (Fahl-

busch et al. 2003) and in the synthesis of fine chemicals
(Leiva de Faria et al. 2000; Volcho et al. 2008; Gaich and
Mulzer 2012; Ishmuratov et al. 2012). Carvone contains

Substrate (mmol)
n.r. not reported
three types of functional groups that can be hydrogenated:

Carveol (10)
C=O, a conjugated C=C and an isolated C=C group. From

carvone hydrogenation, Fig. 2, is possible to obtain dihy-
drocarvone that is a mixture of two stereoisomers; it has a
b
d
a
13

OH
O
Campholenic
Camphene trans-Pinocarveol aldehyde
p-Cymene
O
O
p-Menthene Tricyclene
Pinocamphone
-Pinene
epoxide
OH
-Pinene
Gold-based
heterogeneous
catalysts trans-Carveol
Limonene
OH
O
+ +
OH
DMMBHD
-Terpinene -Phellandrene OH
-Terpinene Terpinolene
Verbenol O
epoxide
OH
OH
OH OH
HTMCPE
O
H
MPCHD
DMCPHP
Fig. 3 Isomerization of monoterpenes and monoterpenoids over gold heterogeneous catalysts
spearmint-like odor and is useful as an additive in food fla- nanoparticles of 1.9 nm. In this case, a deoximation to
vors (Fahlbusch et al. 2003; Winter 2009). Dihydrocarvone carvone and selective hydrogenation of the olefinic C=C
has been obtained by hydrogenation of carvone over Ni, Pt, functional group is carried out (Demidova et al. 2016). Water
Pd, Rh, Ru catalysts (Demidova et al. 2016), typically form- addition to the reaction mixture (0.15–15 mL of methanol,
ing a complex mixture, with dihydrocarvone yield lower 1 vol.%) increased selectivity to carvone with a decrease in
than 30%. the reaction rate and selectivity to dihydrocarvone; possibly
Selective hydrogenation of carvone to dihydrocarvone owing to partial blocking of active catalyst sites and avoid-
was obtained over a 1.9 wt.% Au/TiO2 catalyst (10 mmol ing carvone oxime adsorption and its hydrogenation. Using
carvone, 36 mL solvent, 336 mg of catalyst with 0.3 mol% carvone oxime as a starting material increased the trans-
Au to substrate, 100 °C, hydrogen pressure of 9 bar), with /cis-dihydrocarvone ratio to 4.0, and decreased the reaction
predominant formation of trans-dihydrocarvone. TEM anal- rate compared to carvone hydrogenation; after 23 h carvone
ysis showed that the mean diameter of the gold nanoparticles oxime conversion was 22% compared with a total conversion
was 1.9 nm. The catalytic activity and trans- to cis-isomer after 18 h when carvone was used as starting material. For
ratio strongly depended on the solvent and they increased recycling experiments, after the first reaction run the catalyst
in the following order: 2-propanol < ethanol < methanol. was filtered, washed with ethanol and dried at 373 K before
Selectivity to dihydrocarvone of 62% was achieved at 90% reusing. In the second reaction and at 23 h, carvone oxime
carvone conversion after 13 h in methanol, with a trans- to conversion was 20% and total selectivity to dihydrocarvone
cis-dihydrocarvone ratio of 1.8 (Table 3). The predominant 75% with trans-/cis-dihydrocarvone = 4. The authors con-
formation of the trans-isomer was explained by the specific- cluded that the catalyst was stable and that no significant
ity of carvone adsorption on the catalyst surface (Demidova deactivation was detected during the reaction (Demidova
2014; Demidova et al. 2015). et al. 2016).
Dihydrocarvone can also be obtained by gold-cata-
lyzed one-pot transformation of carvone oxime, which is Hydrogenation of carveol
a key intermediate in carvone synthesis from limonene,
(100 °C, hydrogen pressure of 9 bar, methanol as solvent) Hydrogenation of carveol, Fig. 2, was performed over Au/
over 1.9 ± 0.2 wt.% Au/TiO2 with a mean diameter gold TiO2 catalyst (10 mmol substrate, 36 mL solvent, 336 mg of
13
catalyst with 0.3 mol% Au to substrate, 100 °C and under reactors (Wolf and Schüth 2002). In this context, some gold
H2 atmosphere of 9 bar) (Demidova et al. 2015). The main supported materials have been reported with good stabil-
products were dihydrocarvone, carvotanacetone, as well ity and catalytic activity in pinene isomerization. Gold het-
as carvomenthone. The replacement of the C=O group in erogeneous catalysts used in the transformation of α-pinene
carvone by C–OH in carveol gave a significant decrease in by isomerization are listed in Table 4. Au/γ-Al2O3 catalyst
Au/TiO2 catalytic activity in exocyclic C=C bond hydro- reaches high activity for α-pinene isomerization (higher
genation. trans-Carveol conversion after 21 h was about 33% than 99%), α-pinene conversion did not increase when the
in contrast to the cis-isomer that was 3% (Table 3). The ratio time stream increased from 1 to 6 h, with fairly good and
between dihydrocarvone isomers was similar (1.8) to the stable selectivity to camphene (around 66%), which is the
value obtained for carvone hydrogenation over the same main product (Simakova et al. 2010). The replacement of
catalyst (Demidova et al. 2015). H2 as a carrier gas by N2 did not cause any considerable
changes in α-pinene conversion or selectivity to the main
product. Blank experiments with γ-Al2O3 catalyst gave a
Isomerization very low conversion (2.8%). The results obtained for gas
phase α-pinene isomerization suggest that the reaction pro-
α-Pinene and β-pinene are the most widespread bicyclic ceeds on the Au/γ-Al2O3 catalyst without chemical partici-
monoterpenes, being abundant substrates in the monoterpene pation of H2 and gold is essential for the catalysis. Over 1.5%
fraction of natural essential oils such as pine and eucalyp- AuNi–TiO2/SBA-15 (DP) catalyst, conversion of α-pinene to
tus resins. They allow production of several valuable com- p-cymene was higher than 98% at all temperatures (Ajaiku-
pounds in the fine chemical industry and are widely applied mar et al. 2013); however, it had a great effect on p-cymene
as raw materials for the manufacture of fragrances, flavors, selectivity (the main isomerization product) since selectiv-
vitamins and pharmaceuticals products (Xiang and Luo ity increased with an increase in temperature and reached a
2018). The isomerization of α-pinene (Fig. 3) offers routes maximum (63.2% at 300 °C). The conversion of α-pinene
to two important product families: monocyclic (limonene, was still almost stable after 6 h on stream at all temperatures;
α- or γ- terpinene, terpinolene, p-cymene, β-phellandrene, however, an increase in reaction time and α-pinene inlet con-
menthadiene, allocimene) and polycyclic (camphene, bor- centration gave a decrease in p-cymene selectivity.
nylene, tricyclene) compounds. In order to know the effect of metal function, several
Limonene is used in fragrance, flavor, insecticide and metal loaded catalysts were tested in α-pinene isomeriza-
renewable solvent (Ciriminna et al. 2014). Terpinene has tion under a hydrogen atmosphere (10 mL min−1, 300 °C,
been widely used as a fragrance in cosmetics and house- 0.25 g catalyst with 6 h time on stream and α-pinene flow
hold chemicals, as spice in cookery, and flavoring additive rate of 1.8 mL h−1, WHSV = 6.177 h−1). Loading mono-
in alcoholic beverages and food (Araujo et al. 1996); ter- metallic Au and Cu on TiO2/SBA-15 did not improve the
pinolene is used as a food additive, for example in baked p-cymene selectivity, but in contrast resulted in rapidly
products, ice cream, soft drinks, and candy (Retajczyk and decreasing formation of p-cymene upon increasing time
Wróblewska 2017). p-Cymene is an important product and on stream. In the case of bimetallic catalysts, Au in com-
valuable intermediate and raw material for chemical synthe- bination with Cu, Zn and Ni improved the stability of cata-
sis in industry, used as solvent, heat transfer medium, flavor- lysts towards formation of p-cymene upon an increase in
ing additive, musk perfumes and fragrances and in masking time on stream. In comparison with all other bimetallic
odor for industrial products (Yılmazoğlu and Akgün 2018). catalysts (Au–M-TiO2/SBA-15), AuNi containing catalysts
Camphene is employed as fragrance, solvent, precursor gave maximum selectivity of 63.2% and 54% of p-cymene
in the synthesis of acrylates, resins, isoborneol, isobornyl at 1 h and 6 h time on stream, respectively. AuCo contain-
acetate and camphor; this last used as insect repellent, in ing catalysts behave differently than other catalysts and
the manufacture of films, plastics, medicine and explosives the selectivity of p-cymene decreased rapidly from 49.8 to
(Akgül et al. 2013). 15.2% upon time-on-stream (TOS) 1–6 h respectively. The
Au–M–TiO2/SBA-15 catalysts prepared by the DP method
Isomerization of α‑pinene resulted in a conversion of α-pinene > 98% at 6 h time on
stream and the selectivity towards p-cymene was follow-
The isomerization of α-pinene under gas phase conditions ing the order: Au-Ni–TiO2/SBA-15 > Au-Zn–TiO2/SBA-
presents low activity (in terms of conversion and selectiv- 15 > Au-Cu–TiO 2 /SBA-15 > TiO 2 /SBA-15 > Au–TiO 2 /
ity of desired product); traditional supports such as TiO2 SBA-15 > Cu–TiO2/SBA-15 > Au-Co–TiO2/SBA-15. The
exhibit a limited surface area (around 50 m2 g−1) and might TEM images of the Au-Ni–TiO2/SBA-15 catalyst showed
possibly induce diffusion problems resulting in coke forma- the regular arrangements of hexagonal mesopores (pore
tion and might limit their application in continuous flow diameter 5.95 nm), and gold particles consisted of small
13

16
Table 4 Heterogeneous gold-basd catalytic systems used in gas phase monoterpene and monoterpenoid isomerization
Substrate % Au, catalyst Catalyst Size of GNP, nm T (°C) t (h) Xsubstrate (%) Sproducts (%) References
(mL h−1) mass,
13
mg
α-Pinene 2.2, Au/γ-Al2O3 200 5-8 200 1 99.9 Camphene (66.5), Simakova et al.
(0.4a) limonene (1.2), (2010)
p-cymene (14.6),
tricyclene (8.2)
(0.4a) limonene (1.5), (2010)
p-cymene (14.1),
tricyclene (8.3)
(0.4a,b) limonene (1.8), (2010)
p-cymene (14),
tricyclene (7.7)
250 9.5 250 1 99 Camphene (2.7), Ajaikumar et al.
p-menthene (12.9), (2013)
p-cymene (57.3),
others (27.1)
250 9.5 250 3 98 Tricyclene (0.7), Ajaikumar et al.
camphene (3.1), (2013)
p-menthene (17.5),
p-cymene (50.8),
β-phellandrene
(2.4), others (25.6)
camphene (5.4), (2013)
p-menthene (15.1),
p-cymene (45),
β-phellandrene
(4.7), others (27.1)
camphene (1.1), (2013)
p-menthene (12.5),
p-cymene (60),
β-phellandrene
(1.2), others (24.6)
α-Pinene 1.5, AuNi–TiO2/ 250 9.5 275 3 99 Tricyclene (1.9), Ajaikumar et al.
(1.8) SBA-15 (DP) camphene (1.3), (2013)
p-menthene (13.6),
p-cymene (52.4),
β-phellandrene
(5.7), others (25.1)
(mL h−1) mass,
mg

camphene (2.0), (2013)
p-menthene (14.5),
p-cymene (50.9),
β-phellandrene
(7.1), others (21.4)
250 9.5 300 1 100 Camphene (1.2), Ajaikumar et al.
p-menthene (10.2), (2013)
p-cymene (63.2),
β-phellandrene
(1.6), others (23.8)
camphene (1.6), (2013)

p-menthene (12.9),
p-cymene (55.9),
β-phellandrene
(5.1), others (22.4)
camphene (2.6), (2013)
p-menthene (13.5),
p-cymene (54.0),
β-phellandrene
(5.8), others (20.2)
camphene (1.6), (2013)
p-menthene (12.5),
p-cymene (50.5),
β-phellandrene
(3.7), others (29.5)
1.5, Au–TiO2/SBA- 250 9.5 300 6 98 Tricyclene (4.6), Ajaikumar et al.
15 (DP) camphene (4.4), (2013)
p-menthene (23.8),
p-cymene (26.1),
β-phellandrene
(4.1), γ-terpinene
(3.7), terpinolene
13
(5.5), others (27.8)
17

18
(mL h−1) mass,
13
mg
1.5, AuCu–TiO2/ 250 9.5 300 6 99 Tricyclene (2.9), Ajaikumar et al.

SBA-15 (DP) camphene (1.0), (2013)
p-menthene (17.8),
p-cymene (41),
β-phellandrene
(5.1), terpinolene
(1.2), others (31)
1.5, AuCo–TiO2/ 250 9.5 300 6 100 Tricyclene (8.9), Ajaikumar et al.
SBA-15 (DP) camphene (26.7), (2013)
p-menthene (18.7),
p-cymene (15.2),
β-phellandrene
(1.2), limonene
(1.7), γ-terpinene
(6.1), terpinolene
(9.5), others (12.1)
1.5, AuZn–TiO2/ 250 9.5 300 6 98 Tricyclene (5.1), Ajaikumar et al.
SBA-15 (DP) camphene (2.7), (2013)
p-menthene (16.9),
p-cymene (44.9),
β-phellandrene
(5.2), γ-terpinene
(1.3), terpinolene
(2), others (21.8)
α-Pinene 1.5, AuNi–TiO2/ 250 9.5 300 6 98 Tricyclene (5.1), Ajaikumar et al.
(1.8) SBA-15 (IM) camphene (7.8), (2013)
p-menthene (24.9),
p-cymene (20.1),
β-phellandrene
(3.3), γ-terpinene
(4.9), terpinolene
(7.4), others (26.5)
1.5, AuNi–TiO2/ 250 9.5 300 6 83 Tricyclene (7.9), Ajaikumar et al.
SBA-15 (PM) camphene (35.5), (2013)
p-menthene (6.8),
p-cymene (31.1),
β-phellandrene (3),
limonene (4.2),
others (11.6)
(mL h−1) mass,
mg
3, Au/TiO2 (DP) 250 9.5 300 6 72 Tricyclene (10), Ajaikumar et al.

camphene (37.2), (2013)
p-menthene (5.9),
p-cymene (2.6),
limonene (22.3),
γ-terpinene (3.4),
terpinolene (8.5),
others (10)
1.5, AuCu/TiO2 250 9.5 300 6 98 Tricyclene (10.5), Ajaikumar et al.
(DP) camphene (32.2), (2013)
p-menthene (13.6),
p-cymene (1.2),
limonene (8.8),
γ-terpinene (5.8),
terpinolene (12.5),
others (15.4)
1.5, AuCo/TiO2 250 9.5 300 6 77 Tricyclene (9.8), Ajaikumar et al.
(DP) camphene (34.8), (2013)
p-menthene (2.9),
p-cymene (32.6),
β-phellandrene
(0.8), limonene
(8.1), terpinolene
(1.8), others (9.1)
1.5, AuNi/TiO2 (DP) 250 9.5 300 6 88 Tricyclene (8.5), Ajaikumar et al.
camphene (23.9), (2013)
p-menthene (7.6),
p-cymene (40.2),
β-phellandrene
(2.7), limonene
(3.1), others (14)
α-Pinene 2.2, Au/γ-Al2O3 200 4 ± 0.85 100 < 4.5 100 camphene (~ 65), Solkina et al. (2011)
(0.4a) limonene (~ 15),
others (20)
α-Pinene 2, Au/TiO2 35 2 80 20 100 trans-Pinocarveol Demidova et al.
epoxide (32), campholenic (2014)
13
(0.4c) aldehyde (38),
pinocamphone
(22), trans-carveol
(8)
19

nanocrystals with a mean particle diameter of 7–11 nm
DP synthesized by deposition–precipitation method, IM impregnation method, PM physical mixing, MPCHD (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol, DMCPHP (2R)-
2-[(1R)-2,2-dimethylcyclopent-3-en-1-yl]-2-hydroxypropanal, HTMCPE 2-hydroxy-1-[(1S)-2,2,3-trimethylcyclopent-3-en-1-yl]ethanone, DMMBHD (2R,3R)-6,6-dimethyl-4-methylidenebicy-
located outside of the pore system (Ajaikumar et al. 2013).
The higher selectivity towards p-cymene on nickel con-
In mmol, liquid phase reaction using 10 mL of 1,2-dichloroethane as solvent. All other gas-phase reactions use a space velocity WGSV of 6.177 h−1 and 10 mL min−1 of H2 as gas carrier
Demidova et al.
taining catalyst might be caused by the better dispersion
References
(2014)
of nanoparticles over the support and the ability of dehy-
drogenation of ring opened monocyclic terpene interme-
diates (limonene, terpinolene and γ-terpinene), Table 4.
Au/γ-Al2O3 catalyst exhibited the highest α-pinene conver-
DMMBHD (21)
DMCPHP (11),
HTMCPE (43),
sion (100%); additionally, the main products of α-pinene

MPCHD (25),
isomerization were camphene (60%) and p-cymene (15%),

Sproducts (%)
in agreement with data reported by Simakova et al. (2010).

Au/γ-Al2O3 exhibited high stability (100% conversion) in
250 min of reaction time for α-pinene isomerization; how-
ever, deactivation of catalyst was observed by adsorption
of hydrocarbons over gold species during the reaction.
After regeneration of the catalyst by oxygen treatment
(1 h, 323 K), conversion was 98% and 83% in the second
and third cycle of the reaction (Solkina et al. 2011).
Xsubstrate (%)
Isomerization of α‑pinene epoxide and verbenol

100
epoxide
Liquid phase verbenol epoxide and α-pinene epoxide

isomerization in the presence of Au/TiO2 produced a mix-
ture of monoterpenes and monoterpenoids, Fig. 3. The
main product obtained from α-pinene epoxide isomeriza-
t (h)
tion was campholenic aldehyde, while verbenol epoxide

20
isomerization gave mainly 2-hydroxy-1-[(1S)-2,2,3-tri-

2 as gas carrier
methylcyclopent-3-en-1-yl]ethanone (HTMCPE), Table 4.

Inlet concentration α-pinene/n-octane in % vol, 2200 h−1 space velocity, H
T (°C)
Amination
80
One of the major challenges in fine chemistry is the ami-

Size of GNP, nm
nation of terpenes extracted from biomass to produce

amines which are widely used as agrochemicals, polymers,
in medicine and as intermediates for chemical synthesis.
Amines containing terpenoid fragments have proved to
be important for the development of new pharmaceutical
2
products and their intermediates (Leonard et al. 2015). The

Catalyst
direct amination of alcohols with ammonia is an efficient

mass,
35
mg
way of synthesizing such amines. However, the processes

result in a thermodynamically controlled mixture of pri-
mary, secondary, and tertiary amines, depending on the
clo[3.1.1]heptane-2,3-diol
Substrate % Au, catalyst
structure of the amine and the reaction conditions used,

Verbenol 2,Au/TiO2
but the selectivity can be efficiently modified using cata-

lysts that favor the formation of the primary amines (Pašek

N2 as gas carrier
et al. 1972). Different supported metals such as cobalt,

nickel, copper, platinum, rhenium catalysts have been uti-
epoxide
(mL h−1)
(0.4c)
lized in the amination of alcohols (Ruiz et al. 2017).

b
a
13
Amination of myrtenol the imine with a saturated C–C bond was mainly detected,
with twofold lower amounts of the corresponding amine due
Myrtenol is a bio-active fragrance ingredient isolate of to the hydrogen consumption in C=C bond hydrogenation.
Taxus used in decorative cosmetics, fine fragrances, sham- Unexpected activity in C=C bond hydrogenation seems to be
poos, toilet soaps and toiletries as well as in non-cosmetic related to catalyst modification by the reaction substrates or
products such as household cleaners and detergents (Bhatia to the electronic effect of the substituent on the reactivity of
et al. 2008d); it also has been studied as a therapeutic agent the intermediate via C=C bond polarization. Other amines
and intermediate product in the production of medicines listed in Table 5, benzylamine, phenethylamine, 3,4-dimeth-
(Bejeshk et al. 2019). Myrtenal derived from myrtenol is oxyphenethylamine, 3-aminopyridine, exhibit a selectivity
one of the most prevalent compounds distributed in the higher than aniline to the desired amine. Additional hydro-
Asteraceae family that possess antimicrobial and antifungal gen produced in the reactor may lead to hydrogenation of
activities and it was found to suppress the proliferation of C=C bonds in the target amine or/and corresponding imine,
carcinogenic processes (Burgueño-Tapia et al. 2010). The diminishing the product selectivity.
highest activity in amination of myrtenol over Au/ZrO2 Selectivity strongly depended on the type of support
catalyst was related to the presence of both acidic and basic (Demidova et al. 2013). A nearly complete conversion of
surface sites, Fig. 4. myrtenol was attained only in the presence of Au/ZrO2 and
Table 5 shows that, in the case of amines containing elec- Au/Al2O3 catalysts. Additionally, similar conversion and
tron-donating and -withdrawing groups (aniline, methylani- selectivity were found when the reaction time was increased
line and 4-bromoaniline), the decrease in the selectivity to from 8 to 16 h. Au/ZrO2, Au/CeO2 and Au/MgO exhibited
the desired amine is determined by lower hydrogen trans- high myrtenol conversion, but with similar imine selectiv-
fer to the C = N (Demidova et al. 2018). The formation of ity 35% to the other catalysts. It is important to note that
myrtenal (intermediate product) was detected in the reaction the accumulation of significant amounts of myrtenal dur-
mixture, showing some limitations caused by an additional ing the reaction was observed in the presence of gold on
substituent in the aromatic ring. Additionally, the amine these basic metal oxides, indicating a very slow interaction
yield was demonstrated to be enhanced by introduction of a between myrtenal and aniline, especially in the case of Au/
hydrogen donor such as 2-propanol. In myrtenol amination La2O3. At the same time, non-basic Au/Al2O3 and Au/ZrO2
with an aniline derivative bearing an electron-withdrawing catalysts promoted much faster aldehyde interactions with
group such as 4-bromoaniline, entirely products with a aniline, as well as hydrogen transfer. In comparison with
saturated C–C bond in the initial myrtenol structure were other catalysts, Au/ZrO2 exhibited better selectivity to the
detected in the reaction mixture, even in the absence of an corresponding amine. Gold supported on ceria, lanthania
additional hydrogen source. Among the reaction products, and magnesia exhibited predominantly slow formation of the
R R
O N R NH R
NH N
R-NH2 Myrtenal Imine 1° Amine 1°
OH O N R NH R
Amine 1° Imine 1°
R R OH
NH N Perillyl
aldehyde
Myrtanol Myrtanal Imine 2° Amine 2°
R-NH2 Myrtenol
OH R R
N HN
OH
Amine 2° Imine 2°
Gold-based
heterogeneous R-NH2
catalysts
Nopol Imine 1° Amine 1°
Perillyl alcohol
Fig. 4 Amination of monoterpenic alcohols over gold heterogeneous catalysts.
13

Table 5 Heterogeneous gold-based catalytic systems used in liquid-phase myrtenol monoterpenic alcohols amination.
Substrate R-NH2 Catalyst Size of t (h) Xsubstrate (%) Sproducts (%) References
GNP,
nm
Aniline Au/Al2O3 2.6 8 90 Imine 1° (42), amine 1° (37), Demidova et al. (2013)
imine 2° (2), amine 2° (5)
Aniline Au/Al2O3 2.6 16 95 Imine 1° (39), amine 1° (41), Demidova et al. (2013)
imine 2° (4), amine 2° (5)
Aniline Au/CeO2 2.4 8 76 Imine 1° (35), amine 1° (7), Demidova et al. (2013)
imine 2° (7), amine 2° (21)
Myrtenol Aniline Au/La2O3 2.4 8 80 Imine 1° (16), amine 1° (3), Demidova et al. (2013)
imine 2° (1), amine 2° (2)
Aniline Au/MgO 3.0 8 73 Imine 1° (35), amine 1° (17), Demidova et al. (2013)
imine 2° (3), amine 2° (6)
Aniline Au/ZrO2 2.5 8 96 Imine 1° (36), amine 1° (50), Demidova et al. (2013)
imine 2° (4), amine 2° (4)
imine 2° (3), amine 2° (5)
Aniline Au/ZrO2 2.5 2 ? Imine 1° (39), amine 1° (5), Demidova et al. (2018)
imine 2° (50), amine 2° (3)
imine 2° (10), amine 2° (2)
4-Methylaniline Au/ZrO2 2.5 2 34 Imine 1° (19), amine 1° (1), Demidova et al. (2018)
imine 2° (73),
4-Methylaniline Au/ZrO2 2.5 16 95 Imine 1° (51), amine 1° (4), Demidova et al. (2018)
imine 2° (30), amine 2° (2)
4-Bromoaniline Au/ZrO2 2.5 2 60 amine 1° (43), amine 2° (14) Demidova et al. (2018)
Benzylamine Au/ZrO2 2.5 2 48 Imine 1° (36), amine 1° (13), Demidova et al. (2018)
imine 2° (26), amine 2° (14)
(−)-Myrtenol Phenethylamine Au/ZrO2 2.5 2 40 Imine 1° (63), imine 2° (36) Demidova et al. (2018)
Phenethylamine Au/ZrO2 2.5 8 48 Imine 1° (69), amine 1° (3), Demidova et al. (2018)
imine 2° (20)
3,4-Dimethoxyphenethylamine Au/ZrO2 2.5 16 13 Imine 1° (72), imine 2° (27) Demidova et al. (2018)
3,4-Dimethoxyphenethylamine Au/ZrO2 2.5 16 12 Imine 1° (80), imine 2° (15) Demidova et al. (2018)
3-Aminopyridine Au/ZrO2 2.5 16 19 Imine 1° (21), imine 2° (74) Demidova et al. (2018)
3-Aminopyridine Au/ZrO2 2.5 8 33 Imine 1° (33), amine 1° (2), Demidova et al. (2018)
imine 2° (49)
(−)-Nopol Aniline Au/ZrO2 2.5 8 10 Imine 1° (22), amine 1° (74) Demidova et al. (2018)
(−)-Nopol Aniline Au/ZrO2 2.5 16 40 Imine 1° (19), amine 1° (76) Demidova et al. (2018)
(−)-Perillyl alcohol Aniline Au/ZrO2 2.5 8 98a Imine 1° (28), amine 1° (1), Demidova et al. (2018)
imine 2° (11), amine 2° (11),
aldehyde (2)
Conditions: 1 mmol myrtenol, 1 mmol amination agent, 180 °C, 9 bar of N

2, 10 mL of solvent toluene, 92 mg of catalyst 3% wt. Au
a
160 °C
corresponding imine without significant hydrogen transfer. Nopol is a monoterpenic alcohol used in household prod-
TEM images showed that strong interactions of Au with the uct formulations, agrochemicals, detergents and soaps and
support surface result in the truncated form of particles for synthesized through a Prins reaction between paraformal-
Au/CeO2, Au/ZrO2 and Au/La2O3 catalysts characterized dehyde and β-pinene (Casas-Orozco et al. 2015; Delolo
by the presence of gold cations located in the gold-support et al. 2019). The desired amine from nopol was generated
interface (Demidova et al. 2013). with a selectivity of 76% at nopol conversion of 40%. Pri-
mary monocyclic perillyl alcohol consumption at 180 °C
Amination of nopol and perillyl alcohol was fast and more reactive than bicyclic ones, resulting in
a complex product mixture. However, side reactions at a
The effect of monoterpene alcohol structure was stud- lower temperature of 160 °C were less noticeable, giving
ied using some other primary bicyclic and monocyclic imines and amines as the main products, Table 5.
alcohols, such as nopol and perillyl alcohol, respectively.
13
Conclusions about hydrogenation of limonene, carvone and carveol.

The hydrogenation is carried out mainly under a hydrogen
Monoterpenes and monoterpenoids are a family of chemi- atmosphere and, in some cases, in the presence of carbon
cal compounds that are usually obtained from agro-raw dioxide. Alcohols such as ethanol and methanol are usually
materials; they can be converted into very useful com- chosen as solvents, but not all the reactions use solvents.
pounds that have application in the fine chemical indus- Citral is mainly hydrogenated into geraniol and nerol,
try. Gold heterogeneous catalysts have shown very good limonene into terpinolene, carvone into dihydrocarvone
activity for the transformation of widely spread substrates and carveol into dihydrocarvone and carvotanacetone. In
such as terpenes. Selecting the appropriate support, it is the isomerization of monoterpenes over gold supported
possible to get very selective reactions with substrates catalysts, the type of support has a large influence on the
that contain several functional groups. Other important selectivity of the reaction. In the one-pot myrtenol amina-
parameters in selective reactions are the size of the gold tion, the amine structure noticeably affected the substrate
particles and the adsorption mode of the substrate; typi- conversion and selectivity to the desired amine. In general,
cally, active and selective gold catalysts are obtained with introduction of functional groups, elongation of the car-
a low gold content, because a high gold content promotes bon chain and sterically hindered positions were related to
the formation of large and inactive metal clusters. The a decreasing conversion and increasing selectivity to the
most studied substrates for transformations over heteroge- desired amine; the acid base properties of the support also
neous gold catalysts are limonene and α-pinene, probably affected myrtenol amination.
owing to their large availability in citric fruits and pine Few reports included reusability tests of supported
trees, respectively. Among the monoterpenoids, the most gold catalysts; reported results showed that the materials
used substrates are geraniol, nerol, citronellol, carveol, may have several cycles of use without significant loss of
perillyl alcohol, borneol, menthol and 2-adamantanol. catalytic activity. Furthermore, in some cases the catalyst
Gold heterogeneous catalysts with particle size between 1 reuse was evaluated in the transformation of other substrates
and 10 nm have been supported on Al2O3, SiO2, MCM-41, and not for monoterpene or monoterpenoid processing. It
SBA-15, TiO2, hydrotalcites, C eO2, C, F
e2O3, MgO, Z rO2, was shown in this review that, although monoterpenes and
L a 2O 3. Not only monometallic but also bimetallic gold monoterpenoids are widely available in nature, the research
catalysts with Cu, Ni, Co, Pd and Ru, have shown activ- on their transformation into high value added compounds
ity for monoterpene and monoterpenoid transformations. over heterogeneous gold catalysts is scarce. One of the most
Oxidation is one of the most common ways to increase important challenges for reactions involving monoterpenes
the value of monoterpenes and monoterpenoids. In gen- and monoterpenoids is to achieve a high selectivity towards
eral, the oxidation process of monoterpenes is carried out a specific reaction product. Obtaining a highly selective pro-
by epoxidation of the double bond and allylic oxidation cess is quite complex and still a challenge from the chemical
through the replacement of an acidic hydrogen with an point of view since terpenes have a large number of func-
oxygen atom in the allylic position of the double bond. tional groups that can react. The structure of monoterpenes
Nevertheless, several gold heterogeneous catalysts have is formed by the union of two isoprene molecules units, each
proven to be more efficient during the epoxidation of one having two double bonds; furthermore, the incorpora-
monoterpenes than in the allylic oxidation. The oxidative tion of new atoms such as oxygen or nitrogen increases the
transformation of several monoterpenoid alcohols and amount of functional groups in the same compound and, as
aldehydes over gold heterogeneous catalysts is also a very a consequence, the difficulty of obtaining a product with
efficient process. The catalytic activity of the supported high selectivity. Additionally, for reactions that involve free
materials is higher as long as the particles on a nanoscale radicals, the formation of a single product may be difficult.
are well dispersed on the supports. MgO, ceria, alumina, Important tests that are missing in the catalytic evalua-
titania, hydrotalcite and silicas have been reported as the tion of gold materials are the possibility of reusing them and
most common supports to disperse gold and bimetallic the analysis of their stability under the reaction conditions.
nanoparticles. Different oxidants have been used, the most Research on reaction mechanisms and kinetic analyses of
common being air, O2, H2O2 and TBHP. Usually the reac- monoterpene and monoterpenoid transformations over gold
tions are carried out in liquid phase under mild reaction heterogeneous catalysts will be helpful for a deeper under-
conditions (atmospheric pressure and temperatures not standing the reactions, information that is useful for the
higher than 120 °C), using organic solvents such as tolu- design of reactors where the materials will be used.
ene, acetonitrile and methanol.
The hydrogenation of citral is one of the most common Acknowledgments JAB and ALV acknowledge financial support from
the Universidad de Antioquia and OFA acknowledges the Universidad
monoterpene transformation studies. There are few reports Cooperativa de Colombia.
13

Author contributions JAB, ALV and OFA wrote manuscript and chose Bejeshk MA, Samareh Fekri M, Najafipour H, Rostamzadeh F, Jafari
references, contributed to the discussions. JAB edited the figures and E, Rajizadeh MA et al (2019) Anti-inflammatory and anti-remod-
references. All authors read and approved the final manuscript version eling effects of myrtenol in the lungs of asthmatic rats: histo-
to be submitted. pathological and biochemical findings. Allergol Immunopathol
47(2):185–193
Bhatia SP, Letizia CS, Api AM (2008a) Fragrance material review on
Compliance with ethical standards borneol. Food Chem Toxicol 46(11 Suppl):S77–S80
Bhatia SP, McGinty D, Letizia CS, Api AM (2008b) Fragrance
Conflict of interest The authors declare that the research was con- material review on isoborneol. Food Chem Toxicol 46(11
ducted in the absence of any commercial or financial relationships that Suppl):S182–S184
could be construed as a potential conflict of interest. Bhatia SP, McGinty D, Letizia CS, Api AM (2008c) Fragrance
material review on laevo-carveol. Food Chem Toxicol 46(11
Suppl):S88–S90
Bhatia SP, McGinty D, Letizia CS, Api AM (2008d) Fragrance
material review on myrtenol. Food Chem Toxicol 46(11
References suppl):S237–S240
Bogel-Łukasik E, Bogel-Łukasik R, da Ponte MN (2009) Pt- and Pd-
Abad A, Almela C, Corma A, García H (2006) Unique gold chem- catalysed limonene hydrogenation in high-density carbon diox-
oselectivity for the aerobic oxidation of allylic alcohols. Chem ide. Monatsh Chem Chem Mon 140(11):1361
Commun 30:3178–3180 Bond G, Sermon A (1973) Gold catalysts for olefin hydrogenation.
Abad A, Corma A, García H (2007) Supported gold nanoparticles Transmutation of catalytic properties. Gold Bull 6(4):102–105
for aerobic, solventless oxidation of allylic alcohols. Pure Appl Bond GC, Sermon PA, Webb G, Buchanan DA, Wells PB (1973)
Chem 79(11):1847 Hydrogenation over supported gold catalysts. J Chem Soc Chem
Abad A, Corma A, García H (2008) Catalyst parameters determining Commun 13:444b–445
activity and selectivity of supported gold nanoparticles for the Bone WA, Wheeler RV (1906) The combination of hydrogen and oxy-
aerobic oxidation of alcohols: the molecular reaction mechanism. gen in contact with hot surfaces. Proc R Soc A Math Phys Eng
Chemistry (Eur J) 14(1):212–222 Sci 77(515):146–147
Ajaikumar S, Ahlkvist J, Larsson W, Shchukarev A, Leino A-R, Kordas Boronat M, Concepción P, Corma A, González S, Illas F, Serna P
K et al (2011) Oxidation of α-pinene over gold containing bime- (2007) A molecular mechanism for the chemoselective hydro-
tallic nanoparticles supported on reducible T iO2 by deposition- genation of substituted nitroaromatics with nanoparticles of gold
precipitation method. Appl Catal A 392(1–2):11–18 on TiO2 catalysts: a cooperative effect between gold and the sup-
Ajaikumar S, Golets M, Larsson W, Shchukarev A, Kordas K, Leino port. J Am Chem Soc 129(51):16230–16237
AR et al (2013) Effective dispersion of Au and Au–M (M = Co, Boronat M, Illas F, Corma A (2009) Active sites for H2 adsorption and
Ni, Cu and Zn) bimetallic nanoparticles over T iO2 grafted SBA- activation in Au/TiO2 and the role of the support. J Phys Chem
15: their catalytic activity on dehydroisomerization of α-pinene. A 113(16):3750–3757
Microporous Mesoporous Mater 173:99–111 Burgueño-Tapia E, Zepeda LG, Joseph-Nathan P (2010) Absolute
Akgül M, Özyağcı B, Karabakan A (2013) Evaluation of Fe- and Cr- configuration of (−)-myrtenal by vibrational circular dichroism.
containing clinoptilolite catalysts for the production of camphene Phytochemistry 71(10):1158–1161
from α-pinene. J Ind Eng Chem 19(1):240–249 Bus E, Miller JT, van Bokhoven JA (2005) Hydrogen chemisorp-
Alonso-Gutierrez J, Chan R, Batth TS, Adams PD, Keasling JD, Pet- tion on A l 2O 3-supported gold catalysts. J Phys Chem B
zold CJ et al (2013) Metabolic engineering of Escherichia coli for 109(30):14581–14587
limonene and perillyl alcohol production. Metab Eng 19:33–41 Caballero C, Valencia J, Barrera M, Gil A (2010) Selective hydrogena-
Aprile C, Corma A, Domine ME, Garcia H, Mitchell C (2009) A tion of citral over gold nanoparticles on alumina. Powder Technol
cascade aerobic epoxidation of alkenes over Au/CeO and Ti- 203(2):412–414
mesoporous material by “in situ” formed peroxides. J Catal Cárdenas-Lizana F, Keane MA (2013) The development of gold
264(1):44–53 catalysts for use in hydrogenation reactions. J Mater Sci
Araujo IB, Souza CAM, De-Carvalho RR, Kuriyama SN, Rodrigues 48(2):543–564
RP, Vollmer RS et al (1996) Study of the embryofoetotoxicity Casas-Orozco D, Alarcón E, Villa AL (2015) Kinetic study of the
of α-terpinene in the rat. Food Chem Toxicol 34(5):477–482 nopol synthesis by the Prins reaction over tin impregnated MCM-
Baddour FG, Snowden-Swan L, Super JD, Van Allsburg KM (2018) 41 catalyst with ethyl acetate as solvent. Fuel 149:130–137
Estimating precommercial heterogeneous catalyst price: a sim- Castillejos E, Gallegos-Suarez E, Bachiller-Baeza B, Bacsa R, Serp P,
ple step-based method. Org Process Res Dev 22(12):1599–1605 Guerrero-Ruiz A et al (2012) Deposition of gold nanoparticles on
Bailie JE, Abdullah HA, Anderson JA, Rochester CH, Richardson NV, ZnO and their catalytic activity for hydrogenation applications.
Hodge N et al (2001) Hydrogenation of but-2-enal over supported Catal Commun 22:79–82
Au/ZnO catalysts. Phys Chem Chem Phys 3(18):4113–4121 Charbonneau L, Foster X, Zhao D, Kaliaguine S (2018) Catalyst-free
Bastiani R, Zonno IV, Santos IAV, Henriques CA, Monteiro JLF (2004) epoxidation of limonene to limonene dioxide. ACS Sustain Chem
Influence of thermal treatments on the basic and catalytic proper- Eng 6(4):5115–5121
ties of Mg, Almixed oxides derived from hydrotalcites. Braz J Che M, Bennett O (1989) The influence of particle size on the catalytic
Chem Eng 21:193–202 properties of supported metals. Adv Catal 36:55–172
Becerra J-A, Villa AL (2019) Chapter 1. Clean limonene transforma- Ciriminna R, Lomeli-Rodriguez M, Demma Cara P, Lopez-Sanchez
tions into added-value compounds of fine chemistry using het- JA, Pagliaro M (2014) Limonene: a versatile chemical of the
erogeneous catalysis. In: Taylor JC (ed) Advances in chemistry bioeconomy. Chem Commun 50(97):15288–15296
research, vol 47. Nova Science ublishers, Hauppauge, p 234 Claus P (2005) Heterogeneously catalysed hydrogenation using gold
Becerra J-A, González L-M, Villa A-L (2016) Kinetic study of catalysts. Appl Catal A 291(1):222–229
α-pinene allylic oxidation over FePcCl16-NH2-SiO2 catalyst. J Claus P, Hofmeister H, Mohr C (2004) Identification of active
Mol Catal A 423:12–21 sites and influence of real structure of gold catalysts in the
13
selective hydrogenation of acrolein to allyl alcohol. Gold Bull Gaich T, Mulzer J (2012) 2.7 chiral pool synthesis: starting from
37(3):181–186 terpenes. In: Carreira EM, Yamamoto H (eds) Comprehensive
Corma A, Garcia H (2008) Supported gold nanoparticles as catalysts chirality. Elsevier, Amsterdam, pp 163–206
for organic reactions. Chem Soc Rev 37(9):2096–2126 Gallezot P, Richard D (1998) Selective hydrogenation of α,
Corma A, Iborra S, Velty A (2007) Chemical routes for the β-unsaturated aldehydes. Catal Rev 40(1–2):81–126
transformation of biomass into chemicals. Chem Rev Glaspell G, Hassan HMA, Elzatahry A, Abdalsayed V, El-Shall MS
107(6):2411–2502 (2008) Nanocatalysis on supported oxides for CO oxidation.
Costa VV, Estrada M, Demidova Y, Prosvirin I, Kriventsov V, Cotta RF Top Catal 47(1):22–31
et al (2012) Gold nanoparticles supported on magnesium oxide Gluhoi AC, Bakker JW, Nieuwenhuys BE (2010) Gold, still a sur-
as catalysts for the aerobic oxidation of alcohols under alkali-free prising catalyst: selective hydrogenation of acetylene to ethyl-
conditions. J Catal 292:148–156 ene over Au nanoparticles. Catal Today 154(1):13–20
de Almeida AAC, Costa JP, de Carvalho RBF, de Sousa DP, de Freitas Haider P, Baiker A (2007) Gold supported on Cu–Mg–Al-mixed
RM (2012) Evaluation of acute toxicity of a natural compound oxides: strong enhancement of activity in aerobic alcohol oxi-
(+)-limonene epoxide and its anxiolytic-like action. Brain Res dation by concerted effect of copper and magnesium. J Catal
1448:56–62 248(2):175–187
de Carvalho CCCR, da Fonseca MMR (2006) Carvone: why and Hari TK, Yaakob Z (2015) Recent development of supported
how should one bother to produce this terpene. Food Chem monometallic gold as heterogeneous catalyst for selective
95(3):413–422 liquid phase hydrogenation reactions. Chin J Chem Eng
Degenhardt J, Köllner TG, Gershenzon J (2009) Monoterpene and ses- 23(2):327–336
quiterpene synthases and the origin of terpene skeletal diversity Haruta M (2003) When gold is not noble: catalysis by nanoparticles.
in plants. Phytochemistry 70(15):1621–1637 Chem Rec 3(2):75–87
Delolo FG, Oliveira KCB, dos Santos EN, Gusevskaya EV (2019) Hashmi ASK (2007) Gold-catalyzed organic reactions. Chem Rev
Hydroformylation of biomass-based hydroxyolefins in eco- 107(7):3180–3211
friendly solvents: new fragrances from myrtenol and nopol. Mol Hashmi ASK, Hutchings GJ (2006) Gold catalysis. Angew Chem Int
Catal 462:1–9 Ed 45(47):7896–7936
Demarne FE, Van der Walt JJA (1992) Composition of the essential oil Hutchings GJ (2005) Catalysis by gold. Catal Today 100(1):55–61
of Pelargonium vitifolium (L.) L’Hérit. (Geraniaceae). J Essent Hutchings GJ (2008) Supported gold and gold palladium catalysts for
Oil Res 4(4):345–348 selective chemical synthesis. Catal Today 138(1):9–14
Demidova YS (2014) Terpenoid transformations over gold catalysts. Ishmuratov GY, Yakovleva MP, Valeeva EF, Vydrina VA, Tolstikov
PhD thesis, Åbo Akademi University GA (2012) Monoterpene ketones in the synthesis of optically
Demidova YS, Simakova IL, Estrada M, Beloshapkin S, Suslov EV, active insect pheromones. Russ J Bioorg Chem 38(7):667–688
Korchagina DV et al (2013) One-pot myrtenol amination over Kartusch C, van Bokhoven JA (2009) Hydrogenation over gold
Au nanoparticles supported on different metal oxides. Appl Catal catalysts: the interaction of gold with hydrogen. Gold Bulletin
A 464–465:348–356 42(4):343–348
Demidova YS, Ardashov OV, Simakova OA, Simakova IL, Volcho KP, Khanderi J, Hoffmann RC, Engstler J, Schneider JJ, Arras J, Claus
Salakhutdinov NF et al (2014) Isomerization of bicyclic terpene P et al (2010) Binary Au/MWCNT and ternary Au/ZnO/
epoxides into allylic alcohols without changing of the initial MWCNT nanocomposites: synthesis, characterisation and
structure. J Mol Catal A Chem 388–389:162–166 catalytic performance. Chemistry (Eur J) 16(7):2300–2308
Demidova YS, Suslov EV, Simakova OA, Simakova IL, Volcho KP, Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992)
Salakhutdinov NF et al (2015) Selective carvone hydrogenation Ordered mesoporous molecular sieves synthesized by a liquid-
to dihydrocarvone over titania supported gold catalyst. Catal crystal template mechanism. Nature 359(6397):710–712
Today 241:189–194 Krishna KS, Vivekanandan G, Ravinder D, Eswaramoorthy M
Demidova YS, Suslov EV, Simakova OA, Volcho KP, Salakhutdinov (2010) ZnO: a versatile template to obtain unusual morpholo-
NF, Simakova IL et al (2016) Selective one-pot carvone oxime gies of silica, gold and carbon nanostructures. Chem Commun
hydrogenation over titania supported gold catalyst as a novel 46(17):2989–2991
approach for dihydrocarvone synthesis. J Mol Catal A Chem Lapczynski A, Bhatia SP, Letizia CS, Api AM (2008a) Fragrance
420:142–148 material review on dl-citronellol. Food Chem Toxicol 46(11
Demidova YS, Suslov EV, Simakova IL, Mozhajcev ES, Korchagina supplement):S103–S109
DV, Volcho KP et al (2018) One-pot monoterpene alcohol ami- Lapczynski A, Foxenberg RJ, Bhatia SP, Letizia CS, Api AM
nation over Au/ZrO2 catalyst: effect of the substrate structure. J (2008b) Fragrance material review on nerol. Food Chem Toxi-
Catal 360:127–134 col 46(11 Suppl):S241–S244
Echavarren AM, Hashmi ASK, Toste FD (2016) Gold catalysis-steadily Leandro SR, Mourato AC, Łapińska U, Monteiro OC, Fernandes
increasing in importance. Adv Synth Catal 358(9):1347–1347 CI, Vaz PD et al (2018) Exploring bulk and colloidal Mg/
Elangovan SP, Inoue K, Yokoi T, Okubo T, Kojima A, Ogura M (2008) Al hydrotalcite–Au nanoparticles hybrid materials in aerobic
Solid acid porous materials for the catalytic transformation of olefin epoxidation. J Catal 358:187–198
1-adamantanol. Catal Today 131(1):367–371 Leiva de Faria M, de Magalhães RA, Silva FC, de Matias LGO,
Enache DI, Knight DW, Hutchings GJ (2005) Solvent-free oxidation Ceschi MA, Brocksom U et al (2000) Enantiodivergent syn-
of primary alcohols to aldehydes using supported gold catalysts. theses of cycloheptenone intermediates for guaiane sesquiter-
Catal Lett 103(1):43–52 penes. Tetrahedron Asymmetry 11(20):4093-4103
Fahlbusch KG, Hammerschmidt FJ, Panten J, Pickenhagen W, Schat- Leonard J, Blacker AJ, Marsden SP, Jones MF, Mulholland KR,
kowski D, Bauer K et al (2003) Flavors and fragrances. In: Ull- Newton R (2015) A survey of the borrowing hydrogen
mann’s encyclopedia of industrial chemistry. Wiley-VCH, Wein- approach to the synthesis of some pharmaceutically relevant
heim, pp 73–198 intermediates. Org Process Res Dev 19(10):1400–1410
Fu J, Lu X, Savage PE (2011) Hydrothermal decarboxylation Li Z, Brouwer C, He C (2008) Gold-catalyzed organic transforma-
and hydrogenation of fatty acids over Pt/C. Chemsuschem tions. Chem Rev 108(8):3239–3265
4(4):481–486
13

Liao P-C, Yang T-S, Chou J-C, Chen J, Lee S-C, Kuo Y-H et al Pan M, Brush AJ, Pozun ZD, Ham HC, Yu W-Y, Henkelman G et al
(2015) Antiinflammatory activity of neral and geranial isolated (2013) Model studies of heterogeneous catalytic hydrogenation
from fruits of Litsea cubeba Lour. J Funct Foods 19:248–258 reactions with gold. Chem Soc Rev 42(12):5002–5013
Lima LF, Corraza ML, Cardozo-Filho L, Márquez-Alvarez H, Pašek J, Kondelik P, Richter P (1972) Equilibrium conditions for
Antunes OAC (2006) Oxidation of limonene catalyzed by amination of alcohols and carbonyl compounds. Product R&D
metal(salen) complexes. Braz J Chem Eng 23:83–92 11(3):333–337
Lin S, Vannice MA (1991) Gold dispersed on T iO2 and S
iO2: adsorp- Pattamakomsan K, Ehret E, Morfin F, Gélin P, Jugnet Y, Prakash S
tion properties and catalytic behavior in hydrogenation reac- et al (2011) Selective hydrogenation of 1,3-butadiene over Pd
tions. Catal Lett 10(1):47–61 and Pd–Sn catalysts supported on different phases of alumina.
Lis-Balchin M, Roth G (1999) Citronellic acid: a major component Catal Today 164(1):28–33
in two Pelargonium species (Geraniaceae). J Essent Oil Res Ponec V (1997) On the role of promoters in hydrogenations on met-
11(1):83–85 als; α, β-unsaturated aldehydes and ketones. Appl Catal A
Liston BW, Nines R, Carlton PS, Gupta A, Aziz R, Frankel W et al 149(1):27–48
(2003) Perillyl alcohol as a chemopreventive agent in N-nitros- Prati L, Martra G (1999) New gold catalysts for liquid phase oxida-
omethylbenzylamineinduced rat esophageal tumorigenesis. tion. Gold Bull 32(3):96–101
Cancer Res 63(10):2399–2403 Primo A, Concepción P, Corma A (2011) Synergy between the metal
Liu R, Yu Y, Yoshida K, Li G, Jiang H, Zhang M et al (2010) Physi- nanoparticles and the support for the hydrogenation of func-
cally and chemically mixed TiO2-supported Pd and Au cata- tionalized carboxylic acids to diols on Ru/TiO2. Chem Com-
lysts: unexpected synergistic effects on selective hydrogenation mun 47(12):3613–3615
of citral in supercritical CO2. J Catal 269(1):191–200 Qi S, Cheney BA, Zheng R, Lonergan WW, Yu W, Chen JG (2011)
Lu XH, Lei J, Wei XL, Ma XT, Zhang TJ, Hu W et al (2015) Selec- The effects of oxide supports on the low temperature hydro-
tively catalytic epoxidation of α-pinene with dry air over the genation activity of acetone over Pt/Ni bimetallic catalysts on
composite catalysts of Co-MOR(L) with Schiff-base ligands. SiO2, γ-Al2O3 and TiO2. Appl Catal A 393(1):44–49
J Mol Catal A 400:71–80 Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2013) Low
Macaev FZ (2013) Chapter 7-Bioactive natural products from enan- temperatura CO oxidation on multicomponent gold based cata-
tiomeric carvones. In: Attaur R (ed) Studies in natural products lysts. Front Chem. https://doi.org/10.3389/fchem.2013.00012
chemistry. Elsevier, London, pp 233–267 Retajczyk M, Wróblewska A (2017) The isomerization of limonene
Marmulla R, Harder J (2014) Microbial monoterpene transforma- over the Ti-SBA-15 catalyst-the influence of reaction time,
tions-a review. Front Microbiol. https://doi.org/10.3389/fmicb temperature, and catalyst content. Catalysts 7(9):273
.2014.00346 Rozenbaum HF, Patitucci ML, Antunes OAC, Pereira N Jr (2006)
Martin A, Armbruster U, Decker D, Gedig T, Köckritz A (2008) Production of aromas and fragrances through microbial oxida-
Oxidation of citronellal to citronellic acid by molecular oxygen tion of monoterpenes. Braz J Chem Eng 23:273–279
using supported gold catalysts. Chemsuschem 1(3):242–248 Ruiz D, Aho A, Saloranta T, Eränen K, Wärnå J, Leino R et al (2017)
McEwan L, Julius M, Roberts S, Fletcher J (2010) A review of the Direct amination of dodecanol with NH3 over heterogeneous
use of gold catalysts in selective hydrogenation reactions. Gold catalysts. Catalyst screening and kinetic modelling. Chem Eng
Bull 43(4):298–306 J 307:739–749
Meylemans HA, Quintana RL, Harvey BG (2012) Efficient conver- Schimpf S, Lucas M, Mohr C, Rodemerck U, Brückner A, Radnik
sion of pure and mixed terpene feedstocks to high density J et al (2002) Supported gold nanoparticles: in-depth catalyst
fuels. Fuel 97:560–568 characterization and application in hydrogenation and oxida-
Milone C, Tropeano ML, Gulino G, Neri G, Ingoglia R, Galvagno tion reactions. Catal Today 72(1):63–78
S (2002) Selective liquid phase hydrogenation of citral on Au/ Sell CS (2003) A fragrant introduction to terpenoid chemistry. R
Fe2O3 catalysts. Chem Commun 8:868–869 Soc Chem, p 426
Milone C, Crisafulli C, Ingoglia R, Schipilliti L, Galvagno S (2007) Shahzad SA, Sajid MA, Khan ZA, Canseco-Gonzalez D (2017) Gold
A comparative study on the selective hydrogenation of α, β catalysis in organic transformations: a review. Synth Commun
unsaturated aldehyde and ketone to unsaturated alcohols on Au 47(8):735–755
supported catalysts. Catal Today 122(3):341–351 Silva OA, de Oliveira FRdAM, Lima TC, de Sousa DP, de Souza
Mitsudome T, Noujima A, Mizugaki T, Jitsukawa K, Kaneda K AA, de Freitas RM (2012) Evaluation of the antioxidant effects
(2009) Efficient aerobic oxidation of alcohols using a hydro- in vitro of the isopulegone. Free Radic Antioxid 2(4):50–55
talcite-supported gold nanoparticle catalyst. Adv Synth Catal Simakova IL, Solkina YS, Moroz BL, Simakova OA, Reshetnikov
351(11–12):1890–1896 SI, Prosvirin IP et al (2010) Selective vapour-phase α-pinene
Mohr C, Claus P (2001) Hydrogenation properties of supported isomerization to camphene over gold-on-alumina catalyst.
nanosized gold particles. Sci Prog 84(4):311–334 Appl Catal A 385(1):136–143
Mohr C, Hofmeister H, Claus P (2003a) The influence of real struc- Simakova OA, Davis RJ, Murzin D (2013) Biomass processing over
ture of gold catalysts in the partial hydrogenation of acrolein. gold Catalysts. Springer, p 64
J Catal 213(1):86–94 Solkina YS, Reshetnikov SI, Estrada M, Simakov A, Murzin DY,
Mohr C, Hofmeister H, Radnik J, Claus P (2003b) Identification of Simakova IL (2011) Evaluation of gold on alumina catalyst
active sites in gold-catalyzed hydrogenation of acrolein. J Am deactivation dynamics during α-pinene isomerization. Chem
Chem Soc 125(7):1905–1911 Eng J 176–177:42–48
Monteiro JLF, Veloso CO (2004) Catalytic conversion of terpenes Steeghs MML, Crespo E, Harren FJM (2007) Collision induced dis-
into fine chemicals. Top Catal 27(1):169–180 sociation study of 10 monoterpenes for identification in trace
Nikolaev SA, Zanaveskin LN, Smirnov VV, Averyanov VA, Zanave- gas measurements using the newly developed proton-transfer
skin KL (2009) Catalytic hydrogenation of alkyne and alka- reaction ion trap mass spectrometer. Int J Mass Spectrom
diene impurities in alkenes: Practical and theoretical aspects. 263(2):204–212
Russ Chem Rev 78(3):231–247 Stobiński L, Zommer L, Duś R (1999) Molecular hydrogen interactions
with discontinuous and continuous thin gold films. Appl Surf Sci
141(3):319–325
13
Stratakis M, Garcia H (2012) Catalysis by supported gold nano- Xiang J, Luo Z (2018) Study on the pinene isomerization catalyzed by
particles: beyond aerobic oxidative processes. Chem Rev TiM. Chin J Chem Eng 26(12):2537–2541
112(8):4469–4506 Yang PD, Zhao DY, Margolese DI, Chmelka BF, Stucky G (1998)
Suh Y-W, Kim N-Y, Ahn W-S, Rhee H-K (2001) Redox-mesoporous Generalized syntheses of large-pore mesoporous metal oxides
molecular sieve as a bifunctional catalyst for the one-pot syn- with semicrystalline frameworks. Nature 396:152-155
thesis of campholenic aldehyde from α-pinene. J Mol Catal A Yılmazoğlu E, Akgün M (2018) p-Cymene production from orange
174:249–254 peel oil using some metal catalyst in supercritical alcohols. J
Swift KAD (2004) Catalytic transformations of the major terpene feed- Supercrit Fluids 131:37–46
stocks. Top Catal 27(1):143–155 Yolles RS, Wood BJ, Wise H (1971) Hydrogenation of alkenes on gold.
Thomas AF, Bessière Y (1989) Limonene. Nat Prod Rep 6(3):291–309 J Catal 21(1):66–69
Thompson D (1999) New advances in gold catalysis part II. Gold Bull You K-J, Chang C-T, Liaw B-J, Huang C-T, Chen Y-Z (2009) Selective
32(1):12–19 hydrogenation of α, β-unsaturated aldehydes over Au/MgxAlO
Tracy N, Chen D, Crunkleton D, Price G (2009) Hydrogenated hydrotalcite catalysts. Appl Catal A 361(1):65–71
monoterpenes as diesel fuel additives. Fuel 88(11):2238–2240 Yu N, Ding Y, Lo A-Y, Huang S-J, Wu P-H, Liu C et al (2011) Gold
van der Lingen E (2005) Gold’s other uses. In: The LBMA precious nanoparticles supported on periodic mesoporous organosilicas
metals conference, Johannesburg, pp 75–80 for epoxidation of olefins: effects of pore architecture and surface
Vigneron F, Caps V (2016) Evolution in the chemical making of gold modification method of the supports. Microporous Mesoporous
oxidation catalysts. C R Chim 19(1):192–198 Mater 143(2):426–434
Volcho KP, Rogoza LN, Salakhutdinov NF, Tolstikov GA (2008) Ch. Yue L, Li J, Chen W, Liu X, Jiang Q, Xia W (2017) Geraniol grafted
2 Monotsiklicheskie monoterpenoidy: limonen, karvon i ikh chitosan oligosaccharide as a potential antibacterial agent. Car-
proizvodnye (Part 2/1. Monocyclic monoterpenoids: limonene, bohyd Polym 176:356–364
carvone, and their derivatives). In: Preparativnaya khimiya ter- Zhang Y, Cui X, Shi F, Deng Y (2012) Nano-gold catalysis in fine
penoidov (Preparative chemistry of terpenoids). Art-Avenyu, chemical synthesis. Chem Rev 112(4):2467–2505
Novosibirsk, p 229
Weissermel K, Jurgen Arpe H (2003) Industrial organic chemistry: Publisher’s Note Springer Nature remains neutral with regard to
important raw materials and intermediates. Wiley-VCH, New jurisdictional claims in published maps and institutional affiliations.
York, p 491
Winter R (2009) A consumer’s dictionary of food additives. Random
House Inc., New York, p 608
Wolf A, Schüth F (2002) A systematic study of the synthesis conditions
for the preparation of highly active gold catalysts. Appl Catal A
226(1):1–13
13

Transformation of Monoterpenes and Monoterpenoids Using Gold-Based Heterogeneus Catalysts PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Transformation of Monoterpenes and Monoterpenoids Using Gold-Based Heterogeneus Catalysts PDF

Uploaded by

Copyright:

Available Formats

Brazilian Journal of Chemical Engineering (2020) 37:1–27

Transformation of monoterpenes and monoterpenoids using

Keywords Gold · Monoterpenes · Heterogeneous catalysts · Oxidation · Isomerization · Hydrogenation · Amination

List of symbols met Methionine

Introduction hydrosylation of allenes, hydrothiolation, (oxidative) ring

Citronellal Citronellic acid

-Pinene epoxide Verbenol Verbenone

Fig. 1 Main monoterpenes and monoterpenoids oxidations over gold heterogeneous catalysts

Menth-3-en Menth-2-en Menth-1-en

Carvotanacetone Menthol Isopulegol Citronellal Citronellol 3,7-Dimethyl

Fig. 2 Main monoterpenes and monoterpenoid hydrogenation over gold heterogeneous catalysts

Table 3 Heterogeneous gold-based catalytic systems used in monoterpene and monoterpenoid hydrogenation

Liquid-phase reduction of α,β-unsaturated aldehydes to

(x = Mg/Al molar ratio) calcined at various temperatures

analysis showed that no significant agglomeration of gold

particles occurried when the calcination temperatures were

Mg2AlO (120 °C, 929 kPa), citral conversion was 56.4% and

selectivity to unsaturated alcohol was 97.5%.

the particles in TEM analysis, probably due to high disper-

of about 12 nm were formed. The HRTEM analysis of those

(Liu et al. 2010).

Limonene hydrogenation over Au/TiO2 in Table 3 (10 mmol

substrate, 36 mL solvent, 336 mg of Au/TiO2, 0.3 mol% Au

a conversion of 14% (Demidova et al. 2015). Combined

Pd(2)/TiO2 contains 0.08% Pd wt.

Carvone is a widespread natural monoterpenoid (Macaev

2013) that is used in food and perfumery industry (Fahl-

Mulzer 2012; Ishmuratov et al. 2012). Carvone contains

n.r. not reported

three types of functional groups that can be hydrogenated:

C=O, a conjugated C=C and an isolated C=C group. From

Fig. 3 Isomerization of monoterpenes and monoterpenoids over gold heterogeneous catalysts

250 9.5 275 6 99 Tricyclene (4.1), Ajaikumar et al.

camphene (1.6), (2013)

1.5, AuCu–TiO2/ 250 9.5 300 6 99 Tricyclene (2.9), Ajaikumar et al.

3, Au/TiO2 (DP) 250 9.5 300 6 72 Tricyclene (10), Ajaikumar et al.

nanocrystals with a mean particle diameter of 7–11 nm

sion (100%); additionally, the main products of α-pinene

isomerization were camphene (60%) and p-cymene (15%),

in agreement with data reported by Simakova et al. (2010).

Isomerization of α‑pinene epoxide and verbenol

Liquid phase verbenol epoxide and α-pinene epoxide

tion was campholenic aldehyde, while verbenol epoxide

isomerization gave mainly 2-hydroxy-1-[(1S)-2,2,3-tri-

methylcyclopent-3-en-1-yl]ethanone (HTMCPE), Table 4.

One of the major challenges in fine chemistry is the ami-

nation of terpenes extracted from biomass to produce

products and their intermediates (Leonard et al. 2015). The

direct amination of alcohols with ammonia is an efficient

way of synthesizing such amines. However, the processes

structure of the amine and the reaction conditions used,

but the selectivity can be efficiently modified using cata-

lysts that favor the formation of the primary amines (Pašek

et al. 1972). Different supported metals such as cobalt,

lized in the amination of alcohols (Ruiz et al. 2017).

R-NH2 Myrtenal Imine 1° Amine 1°

Fig. 4 Amination of monoterpenic alcohols over gold heterogeneous catalysts.

Conditions: 1 mmol myrtenol, 1 mmol amination agent, 180 °C, 9 bar of N

Conclusions about hydrogenation of limonene, carvone and carveol.

You might also like

List of symbols met Methionine

-Pinene epoxide Verbenol Verbenone

Fig. 1 Main monoterpenes and monoterpenoids oxidations over gold heterogeneous catalysts

Fig. 2 Main monoterpenes and monoterpenoid hydrogenation over gold heterogeneous catalysts

Table 3 Heterogeneous gold-based catalytic systems used in monoterpene and monoterpenoid hydrogenation

Fig. 3 Isomerization of monoterpenes and monoterpenoids over gold heterogeneous catalysts

Fig. 4 Amination of monoterpenic alcohols over gold heterogeneous catalysts.