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DEDICATION
To the memory of Prof. Jose Barluenga (1940–2016), a pillar of the foun-

dation of modern chemistry in Spain. A man, a giant.
v
CONTRIBUTORS
Enrique Aguilar
Universidad de Oviedo, Oviedo, Spain
Mattijs Baeten
University of Antwerp, Antwerp, Belgium
Jose Barluenga
Diego M. Cannas
School of Chemistry, University of Manchester, Manchester, United Kingdom
Igor Larrosa
Bert U.W. Maes
University of Antwerp, Antwerp, Belgium
Fanyang Mo
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of
Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College
of Chemistry; College of Engineering, Peking University, Beijing, China
Di Qiu
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory
of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College
of Chemistry, Peking University, Beijing; College of Chemistry, Tianjin Key Laboratory
of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin,
China
Anna V. Sberegaeva
Board on Chemical Sciences and Technology, National Academies of Sciences, Engineering,
and Medicine, Washington, DC, United States
Marco Simonetti
Andrei N. Vedernikov
University of Maryland, College Park, MD, United States
Jianbo Wang
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory
of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College
of Chemistry, Peking University, Beijing, China
David Watts
University of Maryland, College Park, MD, United States
ix
x Contributors
Yan Zhang
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of
Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of
Chemistry, Peking University, Beijing, China
PREFACE
We start a new year for this series of Advances in Organometallic Chemistry with
the first volume in 2017, where experts from several areas have prepared five
chapters accounting for the use of organometallic species toward practical
synthesis.
The first chapter corresponds to an invitation to Prof. Barluenga about a
year ago. Sadly for the organometallic community, Prof. Barluenga passed
away last September 2016. In this chapter, coauthored with Aguilar, a com-
prehensive update of the use of group 6 Fisher carbene complexes in organic
synthesis is provided.
N-Tosylhydrazones as carbene source and their use in transition-metal-
catalyzed cross-coupling reactions has emerged in the last decade as a syn-
thetic tool. Wang and coworkers have reviewed this area in Chapter 2,
according to the nature of the metal center employed in the different cata-
lytic systems described to date.
Vedernikov and coworkers have focused in Chapter 3 on a not less
important transformation: the oxidative reaction of late transition metal–
carbon bonds. With no doubt, this functionalization yet constitutes an area
of interest that in spite of decades of study still originates excellent findings
year after year.
The last two chapters are directed toward one of the probably hottest topic
nowadays: the metal-catalyzed coupling reaction, particularly with aryl-
containing substrates. Chapter 4 by Larrosa and coworkers are devoted to
biaryl formation, whereas in Chapter 5 Maes and coworker focus onto
carbon–nitrogen bond formation by means of that strategy.
I would like to acknowledge all the authors for having provided such an
excellent amount of literature accounted for the always exigent reader of this
series. Not less important is the role of the editorial team, Shellie Bryant and
James Selvam; without their input, none of this would have been possible.
PEDRO J. PEREZ
xi
CHAPTER ONE
Group 6 Metal Fischer Carbene

Complexes: Versatile Synthetic
Building Blocks
Barluenga, Enrique Aguilar1
Jose
1
Corresponding author: e-mail address: eah@uniovi.es
We both initiated the preparation and the writing of this review on January 2016,
upon Prof. Barluenga received an invitation by Prof. Pedro Perez. Prof. Barluenga
passed away on September 07, 2016.1 This manuscript is dedicated to honor his
memory.
Contents
1. Introduction 2
2. Synthesis of Group 6 Metal Carbene Complexes 6
3. Release of the Organic Moiety on FCCs 11
4. Applications of Alkyl Carbene Complexes in Organic Synthesis (and of Other
Carbene Complexes in Reactions Where Only the Carbene Carbon Is Involved) 13
4.1 Synthesis of Acyclic Compounds 13
4.2 Synthesis of Three-Membered Carbocycles 16
4.3 Synthesis of Four-Membered Carbocycles 20
4.4 Synthesis of Five-Membered Carbocycles 22
4.5 Synthesis of Six-Membered Carbocycles 27
4.6 Synthesis of Seven-Membered Carbocycles 29
4.7 Synthesis of Heterocycles 32
5. Applications of Alkenyl and Aryl Carbene Complexes 39
5.2 Synthesis of Three-Membered Carbocycles 45
5.5 Synthesis of Seven-Membered Carbocycles 60
5.6 Synthesis of N-Heterocycles 64
5.7 Synthesis of O-Heterocycles 70
6. Applications of Alkynyl Carbene Complexes 72
6.2 Synthesis of Four-Membered Carbocycles 74
Advances in Organometallic Chemistry, Volume 67 # 2017 Elsevier Inc. 1

ISSN 0065-3055 All rights reserved.
http://dx.doi.org/10.1016/bs.adomc.2017.04.001
2 Jose Barluenga and Enrique Aguilar
6.5 Synthesis of Seven- and Eight-Membered Carbocycles 85

6.6 Synthesis of Five-Membered N-Heterocycles 87
6.7 Synthesis of Six-Membered N-Heterocycles 90
6.8 Synthesis of Seven-Membered N-Heterocycles 93
7. Nonheteroatom-Stabilized Carbene Complexes (NHSCCs) 95
7.1 Synthesis of Nonheteroatom-Stabilized FCCs 96
7.2 Early Chemistry of NHSCCs: Cyclopropanation and Metathesis 102
7.3 Applications of Alkynyl NHSCCs as Stoichiometric Reagents in Organic
Synthesis 107
7.4 Stoichiometric or Catalytic Transformations Involving NHSCCs as
Intermediates Synthesized From M(CO)5L and Conjugated Dienynes or
Heterodienynes 113
8. Conclusions, Summary and Outlook 128
Acknowledgments 131
References 131
1. INTRODUCTION
The concept carbene complex denominates the organometallic spe-
cies resultant from the formal combination of a carbene and a metallic frag-
ment. The stability of a carbene complex depends on many factors: the
metal, its oxidation state, the substituents at the carbene carbon, other
ligands attached to the metal … Indeed, some carbene complexes are stable
at room temperature and have been synthesized, isolated, and employed as
reagents or catalysts in many synthetic transformations; on the other hand,
some other, less stable, have been just proposed, detected or, sometimes,
even isolated as synthetic intermediates. Group 6 metal carbene complexes
are typically divided into two major categories:
(a) Schrock-type carbene complexes or Schrock carbenes.2 The major features of these
carbenes are: (i) the metal is in high oxidation state, (ii) they are nucleo-
philic in nature (the carbon atom of the carbene possesses negative charge),
and (iii) they have a relatively short bond distance between the metal and
the carbene carbon. The most relevant carbene complexes of this type are
Mo(VI)- or W(VI)-based carbenes 1 (Fig. 1). Particularly, molybdenum
alkylidenes are very powerful olefin metathesis catalysts, even though their
sensitivity to air and moisture forces to their handling under glove-box or
strict Schlenk techniques. They are usually referred as Schrock catalysts or
Schrock alkylidenes and, some of them are widely employed and com-
mercially available (i.e., Schrock catalyst or Schrock–Hoveyda catalyst).
Group 6 Metal Fischer Carbene Complexes 3
X H XR2
Y M (CO)5M
Z R1 R1
1 2
Schrock carbenes Fischer carbenes
M = Mo, W M = Cr, Mo, W
X = NR2 X = O, N, S
Y = OR3, NR3R4 R1 = alkyl, alkenyl, alkynyl, aryl
Z = alkyl, OR3, NR3R4 R2 = alkyl, aryl, alkanoyl
R1 = alkyl, aryl
R2 = alkyl, aryl
R3, R4 = alkyl, aryl
Fig. 1 Group 6 metal carbene complexes: general structure and representative
examples.
(b) Fischer-type carbene complexes or Fischer carbenes.3 In contrast, for this type
of carbene complexes the metal is in low oxidation state [usually they
are metal(0) complexes], and the pair of electrons in the π-bonding MO
resides mainly on the metal. This, along with the electronegative nature
of the X substituent, has the effect of generating a positive charge on the
carbon atom and, as a result, they are: (i) electrophilic in nature and
(ii) stabilized due to the presence of an electron-donating heteroatom
linked to the carbene carbon (2, Fig. 1).
The general formulae for Schrock and Fischer carbene complexes (FCCs)
are depicted in Fig. 1.
Group 6 metal FCCs are the highly valuable reagents in synthetic organic
chemistry, probably due to the following reasons:
– They are relatively stable organometallic compounds, and in general,
their purification and manipulation are rather easy.
– They can be prepared in multigram scale and can be stored under inert
atmosphere for several months.
– The strongly electron-withdrawing pentacarbonylmetal group allows a
variety of reactivity patterns, which lead to the construction of a large
variety of highly functionalized structures in a regio- and stereoselective
manner. Indeed, de Meijere coined the expression “chemical multitalents”
to label these versatile complexes.4 Additionally, the metal fragment can be
easily removed.
– The possibility of placing chiral auxialiaries in different points of the mol-
ecule makes FCCs as suitable starting materials for diastereo- and
enantioselective synthesis.
Although they have been occasionally proposed as reactive intermediates in

catalytic cycles,5 they are usually employed as stoichiometric reagents, prob-
ably due to the above-mentioned stability provided by the electron-
donating heteroatom. In this sense, chromium complexes have found, by
far, the broadest application of group 6 FCCs probably due to their balance
of reactivity and stability combined with easy accessibility; moreover, tung-
sten carbene complexes are usually more stable while molybdenum com-
plexes are more reactive than their chromium analogs. An additional
reason may lay in the fact that chromium carbene complexes are more prone
toward the insertion of a CO ligand than their tungsten or molybdenum
analogs, due mainly to the differences in metal–CO strength through bac-
kbonding.6 As a consequence, depending both on their counterparts and on
the reaction conditions, the modes of reactivity offered may be either similar
or complementary.
Stabilization to FCCs is provided by the XR2 group, which most com-
monly is either an alkoxy or an amino group, and those carbene complexes
are usually referred to as alkoxy- or aminocarbenes. There are also examples
where acetoxy or thiol derivatives are the stabilizing moieties. Finally,
although less frequent, metalloxy groups have also been employed to stabi-
lize metal carbenes and, in this case, differential reactivity has been found.7
Alkoxy FCCs have been by far the most used among all these categories;
therefore, for the purposes of this review, we will be referring to them when
nothing else is specified.
The electrophilicity displayed by FCCs may be evaluated considering
the 13C NMR chemical shifts of the carbene carbon,8 as well as the high
acidity of the H atoms in α-position to the carbene carbon.9 As shown
in Fig. 2, the chemical shift of the carbene carbon decreases as the
electron-donating ability of the substituents increases. Also in Fig. 2,
the values of pKa of a chromium carbene complex and its analog ester
are compared.
In general, considering the reactive sites presented by group 6 metal
carbene complexes D€ otz has established two major classes of reactions10:
(i) those that involve the participation (cleavage) of the metal–carbene bond
(metal-templated reactions) and (ii) those occurring at the carbene ligand
while the metal–carbene bond remains intact (metal-assisted reactions).
Additionally, a third group of transformations is also relevant; these are
the ones related to classical coordination chemistry and involve ligand
exchange between a carbonyl (or some other) ligand on the metal coordi-
nation sphere. Their special interest is based on the fact that many
Me
Ph OMe NMe2 N
Y Y Y Y
Ph Ph Ph N
Me
Y = Cr(CO)5 399.4 352.0 275.6 219.6 (C6D6)
Y = W(CO)5 357.9 323.9 − 206.6 (C6D6)
Y=O 196.8 167.0 170.7 16.3
d (ppm)
OMe OMe
(CO)5Cr O
Me Me
pKa (Hα) 12.5 25
13
Fig. 2 Properties of carbene complexes vs nonmetallated analogs: C NMR chemical
shifts (CDCl3) and pKa (Hα).
metal-templated reactions are initiated by the dissociation of a carbonyl

ligand followed by coordination of a new reagent or ligand.
General reviews on the chemistry of FCCs have been published rather
periodically, updating the knowledge in the field, either by us11 or by others.12
Additionally, we have also written specific reviews covering topics such as, for
instance, the synthesis of heterocycles,13 multicomponent14 or cycloaddition
reactions,15 or nucleophilic additions.16 On the other hand, other authors have
also offered their own perspectives in the chemistry of FCCs, not only
on synthetic topics17 attending either to the nature of the products formed
(nitrogenated compounds,18 five-membered carbocycles,19 optically active
molecules,20 and aromatic compounds21), the type of reactions involved
(asymmetric synthesis,22 cyclization reactions,23 and cycloaddition reac-
tions24), or the nature of the FCCs involved (polymetallic FCCs,25 metal
glycosylidenes,26 chromium aminocarbene complexes,27 chromium cyclo-
propylcarbene complexes,28 nitrogen-ylide complexes,29 and imidazolidinone
and oxazolidinone chelated carbene complexes30), but also as vehicles for
new discoveries.31 Mechanistic32 and theoretical (physical chemistry,33
computational,34 …) reviews have also been published.
The aim of this manuscript is to provide an updated, general, and com-
prehensive overview of the synthetic usefulness of FCCs. To this end, fol-
lowing this introduction, the first two sections of this manuscript will cover
both the synthetic procedures employed to prepare different types of FCCs
and the methods developed to remove the metal moiety. Then, the
synthetic usefulness of FCCs will be properly discussed, and it has been orga-
nized attending to the nature of the starting carbene complex. Therefore, the
subsequent three sections will be dedicated to: (i) alkyl, (ii) alkenyl and aryl,
and (iii) alkynyl carbene complexes. Besides alkyl carbene complexes, the
first one of these three headings will also include reactions where other
FCCs display the same reactivity under the same reaction conditions; usu-
ally, they will be reactions that only involve the carbene carbon. Addition-
ally, reactions which are specific for other types of FCCs but only involve
the carbene carbon will be included in this section. However, those other
reactions that are specific of either alkenyl or aryl FCCs (or both of them),
because they involve the double bond or the aromatic ring, will be discussed
in the second of those three sections. The same considerations will apply for
alkynyl FCCs and the third of those headings. Additionally, specific sub-
headings have been established attending to the nature of the reaction prod-
ucts: acyclic compounds, carbocycles of different size, and finally,
heterocycles, which have been organized according to the type of the het-
eroatom and to the size of the ring. Finally, the last section before the con-
clusions will cover the chemistry of nonheteroatom-stabilized carbene
complexes (NHSCCs), and will include several subheadings outlining the
synthesis of NHSCCs and its reactivity, mainly depending on the way they
are generated. Along the whole manuscript, reaction mechanisms will not be
discussed in depth in most cases; on the contrary, in general this will be pres-
ented in a rather concise manner, and therefore, in many occasions only the
most relevant intermediates will be shown, or they will not be analyzed at all.
2. SYNTHESIS OF GROUP 6 METAL CARBENE

COMPLEXES
The original method (the “Fischer route”)3 is still the simplest and most
general approach to Fischer-type metal complexes and it involves the
sequential addition of a carbon nucleophile and a carbon electrophile across
a metal-coordinated carbon monoxide ligand (Scheme 1, Via A). The carbon
nucleophiles are usually organolithium reagents (alkyl-, aryl-, alkenyl-, or
alkynyllithium derivatives) which add to hexacarbonyl group 6 metal com-
plexes 3 to afford acyl metallates 4; then, in situ O-alkylation by hard
alkylating reagents such as trialkyloxonium tetrafluoroborates,35 alkyl
fluorosulfonates,36 or alkyl triflates37 leads to alkoxycarbene complexes 5
in yields typically ranging between 60% and 90%. Softer alkylating reagents,
such as alkyl iodides, may be employed under phase transfer conditions.38
Via A
OLi OR2
1
R Li YR2
M(CO)6 (CO)5M (CO)5M Via C
3 4 R1 50%−90% 5 R1 R5ZH
ZR5
(CO)5M
R34NBr Via B R2OH 8 R1
+ O
O− NR34 O
30%−90%
R4COX R5ZH
(CO)5M (CO)5M R4
R1 −40°C
M = Cr, Mo, W R1
6 7
X = Cl, Br
YR2 = R23OBF4, R2O3SCF3, R2O3SF,...
Z = O, S, NH
R1 = alkyl, alkenyl, alkynyl, aryl, R3Si
Scheme 1 Common approaches for the synthesis of group 6 metal FCCs.
In general, the major limitation offered by the Fischer route is related to the
accessibility of both the organolithium reagent and the alkylating reagent.
The preparation of FCCs with elaborated alkoxy groups requires
increasing the nucleophilicity of the acyl metallate species, which may be
accomplished by the exchange of the lithium cation by a tetraalkylam-
monium cation (Scheme 1, Via B). The ammonium acyl metallate 6 is then
treated with acyl halides39 to form an acyloxycarbene 7 (unstable over
40°C), which upon addition of the appropriate nucleophile should
generate the desired carbene complex.40 It is also possible to prepare
amino- and thiocarbene complexes 8 by treatment of alkoxycarbene com-
plexes with the appropriate amine or thiol (Scheme 1, Via C).41
Via A is used mainly for the preparation of alkyl, alkynyl, and aryl alkoxy
carbene complexes. Alkoxy alkenyl FCCs can also be prepared by this route,
although alternative procedures described below are more commonly used.
Via B is used for the synthesis of FCCs bearing alkoxy groups derived from
difficult-to-prepare triflates, and also for aminocarbene complexes.
Alternatively, chromium alkoxy and amino FCCs, 9 and 10, can be syn-
thesized by reacting sodium (or potassium) pentacarbonylchromate with an
acyl halide42 or an amide43 (Hegedus–Semmelhack synthesis, Scheme 2); in
the first case, the acylmetallate initially formed is alkylated at a later stage,
while in the second case the tetrahedral intermediate is treated with tri-
methylsilyl chloride at low temperature.
Alkenylcarbenes 12 have been prepared taking advantage of the strong
acidity of the α-position in alkyl FCCs.44 This procedure is especially useful
O
O OMe
R1 Cl Me3OBF4
Na2[Cr(CO)5] 2 Na+ (CO)5Cr
THF, −78°C R1 Cr(CO)5 H2O, 4°C 1
Cl 9 R
O 14%–65%
O NR22
R1 NR22 Me3SiCl
K2[Cr(CO)5] 2 K+ (CO)5Cr
THF, −78°C R1 Cr(CO)5 THF, −78°C
10 R1
NR22
R1 = alkyl, alkenyl, aryl 20%–93%
NR22 = NMe2, NEt2, NPh2, morpholine
Scheme 2 Synthesis of FCCs from pentacarbonylchromates.
for alkoxy alkyl FCCs 11, bearing structurally complex and/or bulky alkoxy
groups45; a condensation between FCC 11 and the aromatic aldehyde takes
place under mild conditions but with long reaction times (Scheme 3, top).
Special conditions are required with enolizable aldehydes; the aldol addi-
tion is best performed if the aliphatic aldehyde is precomplexed with a Lewis
acid (SnCl4) and the elimination step is achieved by treating adducts 14 with
mesyl chloride and triethylamine (Scheme 3, bottom).46
Alkoxy alkynyl FCCs 18 derived from bulky alcohols (either chiral or
nonchiral) have been prepared from alkoxy FCCs 16 by addition of lithium
alkoxy acetylides 17. The initially formed NHSCCs 19 evolve by 1,3-metal
rearrangement into the reaction products. This approach may be applied to
all three group 6 metals, including the much elusive molybdenum; it also
works efficiently for enolizable carbene complexes (Scheme 4).47
Other strategy, especially useful for the synthesis of allenylidene and cyclic
carbene complexes, has been developed taking advantage of the remarkable
π-acid properties of pentacarbonyl metal complexes (OC)5ML 20. This type
of complexes can be generated by the photochemical cleavage of one carbonyl
ligand in hexacarbonylmetal(0) complexes in the presence of weakly coordi-
nated ligands (such as tetrahydrofuran or triethylamine) (Scheme 5, top). For
instance, methoxy alkenyl FCCs 22 are formed by photolysis of M(CO)6
(M ¼ Cr, W) in the presence of propargyl alcohols 21 in a methanol:THF
solution.48 The proposed mechanism involves the photolytic elimination of
one CO ligand and the rearrangement of η2-alkyne intermediate 23 into
its η1-hydroxyvinylidene isomer 24. Then, loss of water should form
allenylidene intermediate 25 which should be followed by the nucleophilic
addition of the methanol to produce the final products (Scheme 5, bottom).
R3CHO, NEt3 OR2

OR2
(CO)5Cr ClTMS, 20°C (CO)5Cr
12%−85%
R3
11 12
R2OH = EtOH, menthol, 8-Ph-menthol
3
R = alkenyl, aryl, heteroaryl
1) 1 equiv. n-BuLi, −78°C, Et2O

2) 2 equiv. R3CHO/Lewis acid, MsCl (2 equiv.)
Et3N (2.2 equiv.) OMe
−78°C, 2 h OMe
OMe 3) H O 0°C, CH2Cl2 (CO)5Cr
2 (CO)5Cr OH
(CO)5Cr
56%−84% 36%−72%
Me
R3 R3
13 14 15
R3 = Me, n-Pr
Lewis acid = AlCl3, TiCl4, SnCl4
Scheme 3 Synthesis of alkenyl FCCs by condensation with aldehydes.
1) THF, −80°C OR*

2) TMSOTf, −80°C
OMe (CO)5M
3) −80 to 25°C
(CO)5M + R*O Li
R1 65%−90%
16 17 18 R1
1) THF, −80°C 3) −80 to 25°C

2) TMSOTf, −80°C
−
(CO)5M (CO)5M
+
OR* • • OR*
R1 R1
19
M = Cr, Mo, W
R1 = alkyl (2°), alkynyl, aryl
R*OH = trans-2-phenylcyclohexanol, (−)-menthol, (−)-8-phenylmenthol
Scheme 4 Synthesis of alkoxy alkynyl FCCs via nonheteroatom-stabilized carbene
complexes.
Other primary saturated and unsaturated alcohols have been employed instead
of methanol. Higher yields are usually obtained when the pentacarbonyl spe-
cies is photogenerated previously.
This strategy is especially appropriate for the synthesis of cyclic FCCs by
reaction of 20 with terminal acetylenes bearing an adequately placed
hydroxyl group.49 Additionally, tungsten pyranylidene FCCs 27 are
prepared in moderate to good yields from conjugated enyne-carbonyl com-
pounds [i.e., 1-(alkoxycarbonyl)-2-ethynylcycloalkenes 26] in the presence
hn
M(CO)6 M(CO)5L L=THF or Et3N
THF or Et3N
20
OH 1) hn OMe
R1 2) rt
M(CO)6 + (CO)5M R1
R2
MeOH/THF
21 24%−73% 22 R2
M = Cr, W
R1 = H, Me
R2 = Me, alkenyl, aryl
M(CO)6
hn
THF
OH (CO)5M
M(CO)5(THF)
R1
R2 R2 OH
R1
21
23
H
−H2O R1
(CO)5M • MeOH
(CO)5M • • 22
OH
R2
R2 R1
24 25
Scheme 5 Synthesis of alkenyl FCCs 22 initiated by photochemical cleavage of a car-
bonyl ligand.
of stoichiometric amounts of pregenerated W(CO)5THF (Scheme 6).

Regarding the reaction scope, a variety of saturated and unsaturated alkyl
groups can be placed at the alkoxy position. Moreover, 1-carbamoyl-
2-ethynylcycloalkenes have also shown to be suitable starting materials
for this methodology.50
Amino alkenyl FCCs 30, which are not readily accessible by the above-
mentioned procedures, can be prepared in a straightforward manner by ther-
mal metathesis of 2-amino-1,3-butadienes 28 with methoxyphenylcarbene
complexes 29. The scope of the reaction includes all group 6 metals and
moderate to good yields are reached (Scheme 7).51
Additionally, there are many other transformations to prepare specific
FCCs from preexisting FCCs, by reactions involving the carbene ligand.
Usually, the interest of such transformations resides mainly either in the
nature of the transformation or in the structural features of the final products
but not in the fact that FCCs are formed. For those reasons, they have not
W(CO)5⋅THF
W(CO)5
THF, rt−reflux
( )n ( )n
O 0.5−4 h O
35%−75%
OR1 OR1
26 27
R1 = saturated and insaturated alkyl
Scheme 6 Synthesis of pyranylidene FCCs 27 from conjugated enyne-carbonyl
compounds.
O Toluene O
or THF
N OMe
Δ N
+ (CO) M
5
18%−75% (OC)5M
R1 Ph
R2 R1 R2
28 29 30
M = Cr, Mo, W
R1 = alkyl, alkoxy
R2 = H, alkyl
Scheme 7 Synthesis of amino alkenyl FCCs 22 by thermal metathesis of 2-amino-1,3-
butadienes.
been included in this section, but many of them will be discussed along this
manuscript.
3. RELEASE OF THE ORGANIC MOIETY ON FCCs

The reactions of FCCs may be grouped in two types depending on the
presence or not of the metal moiety once the reaction is finished. In the first
case, one additional step is required to remove the metal fragment (or to
release the organic portion) from the reaction products in an efficient man-
ner. There are numerous alternative procedures that allow the transforma-
tion of the metal moiety into different functional groups, adding value to
these systems (Scheme 8, top). Thus, conversion of FCCs 31 into aldehydes
32 is achieved by acidic treatment (hydrobromic acid or triflic acid)52
whereas base (i.e., pyridine) is employed to obtain enol ethers 33 when
the carbene complex bears acidic hydrogen atoms in the α-position.53 Other
transformations include methylenation to enol ethers 34 either with
R1
O
32 OMe
O OMe
H+
R1
R1 [O] Base
38 33
OMe
OMe
(CO)5M Methylenation
SnBu3H R1
31 R1
OMe 34
[H]
Bu3Sn SiMe3H R1
R1
37 OMe
MeO
R1 35
SiMe3
36
R3
N R2 NaBH4, CF3COOH R3
(OC)5Cr 0°C N
R1 70%−96% R2 R1
39 40
R1 = alkyl, aryl
R2 = H, alkyl
R3 = alkyl
Scheme 8 Release of the organic moiety on Fischer carbene complexes.
diazomethane53 or Wittig phosphorus ylides54 or hydrogenation leading to

saturated compounds 35.53,55 Methylenation of aromatic FCCs can be per-
formed with chloromethyllithium to form methylketones.56 Additionally,
the reduction with silicon or tin hydrides leads to silanes 3657 or stannanes
37,58 respectively. However, the most common strategy to remove the
metal fragment involves the conversion of alkoxy FCCs into their analogous
esters 38 by oxidation either with cerium ammonium nitrate (CAN),59 pyr-
idine N-oxide (PNO),60 dimethyldioxirane,61 dimethylsulfoxide,8 or by air
oxidation, which may be promoted by the anion fluoride.62 Most of these
reagents also oxidize amino FCCs to amides. Finally, reduction of amino
FCCs 39 to amines 40 is achieved with metal hydrides (Scheme 8,
bottom).63
4. APPLICATIONS OF ALKYL CARBENE COMPLEXES IN

ORGANIC SYNTHESIS (AND OF OTHER CARBENE
COMPLEXES IN REACTIONS WHERE ONLY THE
CARBENE CARBON IS INVOLVED)
This section covers the reactions of alkyl carbene complexes as well as
transformations involving other types of FCCs, but where only the carbene
carbon takes part in the reaction. Some of them are exclusive for specific
types of FCCs.
4.1 Synthesis of Acyclic Compounds

Hegedus has described that metal-coordinated ketenes are easily generated
by photolysis of chromium FCCs64; its subsequent reaction with nucleo-
philes allows the synthesis of carboxylic acid derivatives. For instance,
α-amino esters 4165 (Scheme 9, top) and dipeptides 44 (Scheme 9, bottom)
are formed by photolysis of amino FCCs 39 and 42 in the presence of
R3 O R3
N R2 hn, CO, MeOH N
(CO)5Cr MeO R2
R 1 45%−98% R1
39 41
R1 = H, alkyl, aryl
R2 = R3 = PhCH2, Me, Et
O
Also,
R3 Bn Me
N R2 N N N N
(CO)5Cr = (CO)5Cr , (CO)5Cr , (CO)5Cr , (CO)5Cr
R1 ( )n
39 n = 1, 3, 4, 10
Ph
O R3
O hn, 0°C,
H OR2
N O 3 THF, 50−80 psi CO R1 N
+ R OR 2 H
(CO)5Cr Ph
55%−88% N O
R1 NH2 dr: 74:26 to 98:2
42 43 O
44
1
R = H, CH2CO2t-Bu, PhCH2, CH2KCH–CH2
R2 = t-Bu, Me
R3 = H, Me, Ph, PhCH2, CH3CH(OH), 2-indolyl
Scheme 9 Synthesis of α-amino esters by photolysis of aminocarbene complexes.

alcohols and α-amino esters 43, respectively. In the latter case, double ste-
reoselection applies when optically active chromium amino FCCs react in
the presence of esters of optically active α-amino acids; the (S)(S) dipeptide is
the matched pair while the (R)(S) is the mismatched pair. Excellent yields
and good diastereoselectivities are usually obtained.66
In a similar manner, the photochemical reaction of chromium alkoxy
FCCs 45 and sulfur ylides 46 leads stereoselectively to 2-acylvinyl ethers
47. Interestingly, the same products are formed in similar E/Z selectivity
under thermal conditions but with longer reaction times. MeCN is the opti-
mal solvent as it favors solubility of the reagents and produces cleaner reac-
tion mixtures, although better diastereoselectivities can be obtained with less
polar solvents67 (Scheme 10, top). In a related process, the reaction of alkoxy
FCCs with α-haloester or α,α-dihaloester lithium enolates 49 at 78°C,
followed by quenching with silica gel leads 1:1 to mixtures of Z and E
α-substituted enol ethers 50; acid hydrolysis of the enol ether mixtures 50
generates β-keto esters 51 in high yields (75%–90%). However, this
approach is restricted to aromatic FCCs68 (Scheme 10, bottom).
OR2 O
OR2
+ − O MeCN, hn
(CO)5Cr + S
48%−90% R1 R3
R1 R3 E/Z = 1:1 to 100:0 H
45 46 47
R2 = alkyl, aryl Ph
R1 = Me, PhCH2, , , ,
R3 = MeO, t-BuO, Ph
OMe
(CO)5Cr
THF OMe O O O
Ar
48 −78°C to rt H3O+
+ Ar OR2 Ar OR2
OLi
73%−95% 75%−90%
1 1 1
R E/Z = 1:1 R R
OR2
50 51
X
49
Ar = aryl, heteroaryl
R1 = H, C4H9, Cl
R2 = Me, Et
X = Cl, Br
Scheme 10 Synthesis of 2-acylvinyl ethers and β-keto esters.
Tungsten alkoxy FCCs 52 undergo the nucleophilic attack of zinc-

chelated glycine-derived enolates 53 to straightforward produce (E)-β-
alkoxy-α,β-unsaturated esters 54 in a stereoselective manner (Scheme 11).
The reaction works fine for aryl- and alkyl-substituted FCCs; however,
the former produce E/Z-diastereomeric mixtures while the latter lead
exclusively to the E-isomers.69
Alkoxy aryl FCCs 48 are able to react with 2-unsubstituted benzoxazoles
55 under basic conditions in toluene at high temperatures leading to
2-substituted benzoxazoles 56 through C–H bond functionalization. The
reaction should proceed via benzoxazole deprotonation followed by nucle-
ophilic addition to the carbene carbon; noteworthy, the tetrahedral interme-
diate evolves by loss of the metal fragment rather than the more common
alkoxy group elimination. Such behavior is attributed to the presence of
an acidic proton in the reaction media70 (Scheme 12).
1,2-Diarylethanones 58 are formed in moderate to good yields by the
coupling of aromatic N-tosylhydrazones 57 with chromium alkoxy aryl
FCCs 48, under thermal conditions and in the absence of any catalyst. This
transformation displays a wide scope regarding the electronic nature of the
aromatic groups in both coupling partners; additionally, regarding the ste-
rics, ortho-substitution at the FCC is tolerated71 (Scheme 13).
LHMDS, ZnCl2
THF
OR2 −78 to −50°C , 1.5 h
R1 CO2R3
(CO)5W 0°C, 1.5 h
+ H 2N COOR3
R1 63%−77% R2O
52 53 R1 = aryl, E/Z = 1.1:1 to 2.3:1 54
R1 = alkyl, aryl R1 = alkyl, E/Z = >99:1
R2 = Me, Et
R3 = Me, t-Bu, Bn, 2-butenyl
Scheme 11 Synthesis of (E)-β-alkoxy-α,β-unsaturated esters from tungsten alkoxy FCCs.
LiOtBu (2 equiv.)
toluene,
OMe N MeO N
100°C or 120°C
(CO)5Cr +
Ar O 23%−90% Ar O
X X
48 55 56
X = alkyl, MeO, F, Cl, Br
Scheme 12 Synthesis of 2-substituted benzoxazoles from alkoxy aryl FCCs.
1) K3PO4 (2 equiv.)
OMe toluene, 90°C or 110°C O
2) 2M HCl, THF, 60°C
(CO)5Cr + Ar1 NNHTs Ar1
Ar
Ar 33%−78%
48 57 58
Ar1 = aryl
Scheme 13 Synthesis of 2-substituted benzoxazoles from alkoxy aryl FCCs.
4.2 Synthesis of Three-Membered Carbocycles

The development of appropriate conditions for the cyclopropanation reac-
tion has been one of the main objectives in the chemistry of FCCs, since
shortly after their discovery.72,73 Indeed, the outcome of the process is
highly dependent on the nature of both the olefin and the carbene complex.
For instance, regarding the carbene complex, amino FCCs usually do not
partake in cyclopropanation reactions because of their inertness, although
some exceptions have been reported (vide infra); on the other hand, alkoxy
FCCs are involved in most cyclopropanations, and their behavior against
electronically different olefins is summarized in Scheme 14.
Thus, for electron-deficient olefins and alkoxy FCCs, the reaction
requires quite energetic conditions with temperatures in the 80–140°C
range, and sometimes the olefin behaves also as solvent. Good yields
of cyclopropanes 59 are usually obtained but as mixtures of diaste-
reomers; remarkably, the selectivity depends on the metal employed.
This fact suggests that the cyclopropanation occurs within the metal
coordination sphere and discards the involvement of free carbene species.
Occasionally, olefins 60 and 61 are obtained as by-products; they may be
explained by formal insertion into the C–H olefin bond and cyclopro-
pane ring opening. A mechanism to account for the observed results
has been proposed.74 More recently, the cyclopropanation of electron-
deficient olefins has been achieved at room temperature by using trans-
metallation to Ni75 or Cu.76
The cyclopropanation of electron-deficient alkenes can be also thermally
achieved with chromium alkoxy alkynyl FCCs 65 to form donor–acceptor
alkynylcyclopropanes 66 in moderate yield and good diastereoselectivity
ratio77 (Scheme 15). The major diastereomers display a cis relationship
between the electron-withdrawing group and the triple bond; this fact
has been used advantageously to prepare oxepinones and azepinones by
gold-catalyzed cycloisomerizations.78
Z R1 OR2 Z OR2 Z OR2

+ +
Δ
Z R1 R1
59 60 61
(49%−89%) (2%−24%) (1%−3%)
OR2
(CO)5M OR2
X
R1
5 Z = electron-withdrawing group
35°C R1
R1 = alkyl, aryl, alkenyl 62 X = electron-donating group
(46%−62%) C = nonactivating group
X R1 OR2
50°C X 63
100 atm CO
(60%−70%)
OR2 C R1 OR2
(CO)5M
5 R1 Δ C 64
1
R = alkenyl, heteroaryl (60%−88%)
Scheme 14 Synthesis of cyclopropanes by [2+1]-reaction of FCCs and alkenes.
OMe OMe
(CO)5Cr 90°C, THF
Z
+
30%−70% Z
dr = >95:<5 to 91:9 R1
R1
65 66
R1 = alkyl (1°, 3°), alkenyl, aryl, TMS

Z = CO2Me, CONMe2, PO(OEt)2, CN
Scheme 15 Synthesis of “push–pull” alkynyl cyclopropanes by reaction of chromium
alkynyl FCCs and electron-deficient alkenes.
On the other hand, for electron-rich olefins metathesis products 62 are

obtained instead of cyclopropanes 63, unless the reaction is performed under
a high pressure of carbon monoxide (Scheme 14); this fact indicates that the
cyclopropanation of electron-rich olefins follows a different pathway. How-
ever, very recently, the cyclopropanation at low temperature and in the
absence of CO of an electron-rich olefin by an heteroatom-stabilized
FCC has been reported79 (Scheme 16); thus, the mixing of β-substituted
ketone lithium enolates 67 and chromium methoxy FCCs 48 leads
diastereoselectively to cyclopropanols 68 in an efficient protocol. Adducts
1) THF, −78 to 20°C

2) THF + i-Pr2NH removal
3) TMSCl, THF, or MeOTf, Et2O R1
OMe OLi −78 to 20°C R2
(CO)5Cr + Ar
R1 72%−84% R3O
Ar R2 OMe
48 67 68
R1 = Me, Et
R2 = alkyl (1°, 2°), aryl, heteroaryl
R3 = TMS, Me
Scheme 16 Synthesis of substituted methoxycyclopropanes by reaction of chromium
aryl FCCs and β-substituted ketone lithium enolates.
yields are increased when cyclopropanol decomposition during purification

is avoided by performing in situ TMS- or Me protection.
For nonactivated olefins, examples of intramolecular cyclopropanation
have been disclosed,80 including an strategy to synthesize 2-oxabicyclo
[3.1.0]hexan-3-ones 71 involving acyloxy FCCs 72; these reaction interme-
diates are prepared in situ from tetramethylammonium chromates 69
and β,γ-unsaturated acyl chlorides 70 (Scheme 17). The acylation/
cyclopropanation sequence takes place at 10°C, in good yields and with
exo selectivity.81 The high stereoselectivity reached has allowed the prepa-
ration of cycloheptadiene derivatives via Cope sigmatropic rearrangement
on cis-divinyl cyclopropanes.
However, the intermolecular approach to cyclopropanes 64 (Scheme 14)
fails for simple alkyl-substituted olefins. Barluenga demonstrated, for the
first time, that intermolecular cyclopropanation of electronically neutral
alkenes can be performed by chromium alkoxy alkenyl FCCs containing
an aryl group attached to the β-position or by chromium alkoxy heteroaryl
FCCs. Interestingly, both cyclic and acyclic olefins undergo cyclopro-
panation with high diastereoselectivity and functionalization at the olefin
allylic position is tolerated.82 As an example, the cyclopropanation of
1-hexene with (methoxy)(2-ferrocenylethenyl)carbene 73 is carried out
in DMF at 152°C to furnish cyclopropane 74 in high yield and 97% de;
cyclopropane carbaldehyde 75 has been prepared by ozonolysis of the
alkenyl function (Scheme 18). Additionally, cyclopropanols can be obtained
when 2-haloethoxy alkenyl FCCs are employed.83
On the other hand, tungsten alkoxy alkynyl FCCs 76 are able to react
with electronically nonactivated olefins such as fulvene derivatives 77,
leading to the [2+1]-cycloadducts 78 with preferential exo-selectivity
(dr: 3:1 to >30:1), and complete E-selectivity for unsymmetrical fulvenes
(Scheme 19).84
Cl O
O
ONMe4 R2
R2 −10°C, CH2Cl2
O
(CO)5Cr
+ R3
R1 23%−85% R3 R1
R4 R4
69 70 71
R1 = alkyl, alkenyl, aryl R2 O

R2 = H, Me, Bn
R3 = H, Bn R3 O
R4
R4 = H, alkyl, alkenyl (CO)5Cr
R1
72
Scheme 17 Synthesis of 2-oxabicyclo[3.1.0]hexan-3-ones from acyloxyl FCCs.
1) O3, CH2Cl2
OMe DMF, 4% BHT MeOH, −78°C
152°C, 0.5 h Bu OMe 2) Me2S, 20°C Bu OMe
(CO)5Cr Fc
88% Fc 59%
H H CHO
73 97% de 97% de
74 75
Fc = Ferrocenyl
Scheme 18 Synthesis of cyclopropane 74 by intermolecular reaction between
chromium alkoxy alkenyl FCC 73 and 1-hexene, and its oxidation to cyclopropane-
carbaldeyde 75.
R1
OMe R2 R3 R2 R3
(CO)5W 60°C, THF
+
65%−73%
exo/endo 3:1 to >30:1 OMe
R1
76 77 78
Scheme 19 Synthesis of alkynylcyclopropanes 78 by reaction between tungsten alkoxy
alkenyl FCCs 76 and fulvenes.
The cyclopropanation reaction is rather elusive for amino FCCs, espe-

cially against electron-deficient alkenes, because of decomposition of the
reaction products to ring-opening species, and also because of the high
stability of amino FCCs themselves. Therefore, the strategies employed
to achieve cyclopropanation with amino FCCs are based on reducing such
stability. For instance, the first example reported involves pyrrolocarbene
complex 79, which is more reactive than conventional aminocarbenes
because of the delocalization of the unshared pair of electrons at the nitro-
gen atom through the aromatic pyrrole ring; indeed, FCC 79 produces
cyclopropylpyrroles 80 in moderate to good yields and with low dia-

stereoslectivities85 (Scheme 20, top). The pyrrole group has been trans-
formed into a primary amine at a later stage. A second example uses
dialkylamino alkoxycarbonyl FCCs 81, where the electron-withdrawing
effect of the alkoxycarbonyl group increases the reactivity of the FCC.
The corresponding cyclopropanes 82 are formed by reaction with cyclic
and acyclic nonconjugated olefins in refluxing toluene in moderate to good
yields and usually with high diastereoselectivities86 (Scheme 20, bottom).
4.3 Synthesis of Four-Membered Carbocycles

The reactivity of FCCs against olefins changes completely when photo-
irradiation is applied. Thus, the photolysis of chromium alkoxy FCC 13
in the presence of simple olefins leads to cyclobutanones 83 in excellent
yields via photochemically generated ketenes (Scheme 21, top). The high
regioselectivity observed corresponds to that resulting from attack of the
more nucleophilic olefin carbon on the electrophilic ketene carbonyl car-
bon. The reaction is also stereoselective; in many cases, a single diastereomer
is formed. Additionally, for 1,2-disubstituted alkenes the stereochemistry of
the olefin is maintained in the cyclobutanone product. However, the [2+2]-
cycloaddition does not take place for electron-poor olefins, such as methyl
acrylate or acrylonitrile, under the reaction conditions.87 On the other hand,
Z
Z 100°C, THF/DBTH
N +
N
(CO)5M 66%−90%
dr 1.6:1 to 3.4:1 R1
79 R1 80
M = Mo, W
R1 = Me, Ph
Z = CO2Me, CN
NR22 111°C, toluene R3

(CO)Cr R3 24−50 h
+
OR1 35%−70% NR22
O de >95 R1
81 82
R1 = Me, t-Bu
R2 = Me, Bn; also HNR22 = morpholine
R3 = alkyl, aryl
Scheme 20 Cyclopropanation reactions involving group 6 metal amino FCCs.
MeCN MeO
OMe Me
hn (450 W)
(CO)5Cr + R1 R1
Me 13%−96%
dr 5:1 to >95:<5 O
13 83
R2O
OR2 Et2O, CO
R1
(CO)5Cr hn (450 W)
+
R1 37%−96%
dr: 4:1 to 20:1 O
45 84
R1 = alkyl (1°, 2°), alkenyl, aryl
R2 = Me, Et, PhCH2, TMS
R3 Et2O, CO R3 H
O ( )n hn (450 W)
(CO)5Cr ( )n
29%−88%
Me O
O
n = 1, 2 85 86
R3 = H, Me, Et
O
O
O CH2Cl2, CO R2O
OR2 O R1 N
hn (450 W)
(CO)5Cr + N
R1 50%−67% Ph
Ph de: 86% to >97% O
45 87 88
R1 = alkyl (1°, 2°), aryl
R2 = Me, PhCH2
R1−R2 = −(CH2)4−
Scheme 21 Synthesis of cyclobutanones from FCCs and olefins.
the employment of cyclic conjugated dienes, such as cyclohexadiene, or of

chromium alkoxy FCCs 85 having remote double bonds in the alkoxy
group allows the synthesis of bicyclic cyclobutanones 84 or 86 in good yields
and in a highly stereo- and regioselective manner88 (Scheme 21, middle).
When the photolysis of the chromium FCCs 45 is performed in the pres-
ence of optically active (S)-ene-carbamate 87, under 90 psi of CO pressure,
optically active cyclobutanones 88 are readily obtained in moderate to good
yields and with high control of both the relative and the absolute stereo-
chemistry. This [2+2]-cycloaddition failed for a trans-ene-carbamate but
was performed successfully for a gem-disubstituted ene-carbamate89
(Scheme 21, bottom).
Usually chromium methoxy FCCs 9 react thermally with silyl-

substituted internal acetylenes to produce highly stable silyl vinyl ketenes.90
However, a formal [2+1+1]-cycloaddition occurs when TIPS-substituted
furan-2-yl or cyclopropyl acetylenes are employed, and cyclobutenones
89 have been isolated as sole reaction products.91 Silyl vinyl ketenes 90 have
been identified as precursors of the reaction products (Scheme 22).
4.4 Synthesis of Five-Membered Carbocycles

Transmetallation from group 6 metals to metals of other groups in the peri-
odic table has emerged as a powerful strategy to modulate the reactivity of
FCCs.92 Thus, chromium aryl FCCs 48 react with two units of an internal
alkyne in the presence of [Ni(cod)2] to provide highly substituted
cyclopentadiene derivatives in a [2+2+1] cyclization.93 The electronic
properties of the acetylene determine the regiochemistry of the cyclization
for nonsymmetrical alkynes. Thus, a sole isomer of unsymmetrical adducts
91 is obtained for 1-phenyl-1-propyne whereas symmetrical cyclopen-
tadienes 92 are formed for methyl 2-butynoate (Scheme 23).
On the other hand, chromium cyclopropyl FCC 93 undergo cycload-
dition to alkynes leading to cyclopentenone derivatives 94 in good yields
(Scheme 24, top).94,95 The reaction tolerates a variety of functional group
and proceeds with high regioselectivity being the large substituent at the
alkyne placed adjacent to the cyclopentenone carbonyl group. The pro-
posed mechanism should involve the initial elimination of CO, followed
subsequently by complexation of the metal carbonyl species to the alkyne
and by insertion of the alkyne to form metallacycle 95. This species should
open to form alkene-coordinated alkenyl carbene complex 96, which has
R2 R1
OMe R2
Benzene, 80°C MeO
(CO)5Cr +
R 1 66%–73%
TIPS O TIPS
9
OMe 89
R1 = n-Bu, Me
2
R2 = c-Pr, 2-furyl R
R1
C TIPS
O
90
Scheme 22 Synthesis of cyclobutenones from FCCs and TIPS acetylenes.
Ph
Me
OMe
Ph Me
Ar
OMe Ni(cod)2 48%−51% Ph
MeCN Me
91
(CO)5Cr Ar −10 to 20°C
Me
MeOOC
48 MeO2C Me OMe
51%−56%
Ar
MeOOC
Ar = Ph, 4-methoxyphenyl
Me
92
Scheme 23 Synthesis of cyclopentadienes via [2+2+1]-cycloaddition reactions.
O
RL Aqueous dioxane
Cr(CO)5
reflux RL
+
OMe 42%−79%
dr = 7:1 to >99:1 OCH3
93 RS RS 94
RL = alkyl, alkenyl, aryl
RS = H, alkyl, aryl
RL RL RS RL
Cr(CO)5 −CO (CO)4Cr
+ Cr(CO)4
OMe MeO RS
93 RS OMe
95
Cr(CO)3
Cr(CO)4 Cr(CO)4
O
RL
RL
RL
MeO RS MeO RS MeO
RS
96 97 98
O
RL RL
O O Cr(0)
RL
H2O
RS RS 94
OMe OMe RS OMe
Cr(CO)3 Cr(CO)3 101
99 100 + ethylene + Cr(0)
Scheme 24 Reaction conditions and mechanism for the synthesis of cyclopentenones.

been found to be an intermediate for this reaction.95 Then, a cyclopropane

ring opening (i.e., a 1,5-alkyl shift, to 97) should be successively followed by
CO insertion (to 98), conversion to dienyl complex 99, and the closure of
the ring (to 100). Finally, loss of ethene is proposed to generate
cyclopentadienone intermediate 101, which should be transformed into
the final cyclopentenone vinylogous ester derivatives 94 by a reduction pro-
cess, carried out by the low-valent chromium fragment under the aqueous
reaction conditions (Scheme 24, bottom). Interestingly, the transformation
of metallacyclooctadienone 98 into bicyclic system 100 can be seen as a for-
mal olefin insertion into the metal–carbonyl bond.
Intramolecular versions of this reaction have proved to be especially effi-
cient. For instance, good to excellent yields have been reached for
cyclopentenones fused to oxygen heterocyclic rings, such as cyclopenta[b]
pyran-6(2H)-ones 103 (Scheme 25, top). Indeed, in these intramolecular
approaches, the stereochemistry can be controlled by placing a stereogenic
carbon in the tether; in any case, the diastereoselectivity strongly depends
both on the position of the chiral center and on the ring size of the hetero-
cyclic ring formed.96 This reaction has been employed in a formal total syn-
thesis of ()-vitamin D3.97
Moreover, alkylidenecyclopentenones, such as 104, or alkoxyalkyl-
cyclopentenones are obtained, depending on the leaving group ability of
the propargyl substituent, when propargyl alcohols are employed as acety-
lenes (Scheme 25, bottom).
O
Cr(CO)5 R2 Toluene/water R1
reflux
H
O 62%−72%
dr = 50:50 to 94:6 R2 O
102
R1
103
R1 = H, Ph, Me
R2 = Me, Ph
Ph O
Cr(CO)5 Toluene/water
reflux Ph
+
OMe 65%
93 AcO 104 OCH3
Scheme 25 Synthesis of bicyclic cyclopentenones 103 and alkylidenecyclo-
pentenone 104.
Another random document with
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meeting of the Baking Society decided that bread should be supplied
to shops only of customer societies.
A RIGHT OF WAY CASE.
A paragraph of a rather peculiar character appears in the last
minute for 1885. At that time the committee were in the thick of their
preparations for the new bakery, and must have been extremely
busy. Nevertheless, some time during the month, a letter was
received which must have worried the secretary and the sub-
committee not a little. It was signed “Thomas Mann,” and was as
follows:—
“Gentlemen,—As aiders and abettors in the Kilbarchan Right of Way case I
have to inform you that the expenses, amounting to £850. are still unpaid, and
that unless an arrangement is made with my law agent within eight days an
action will be raised against you in the Court of Session for the full amount.”
The manager had replied wishing to know on what authority Mr
Mann had taken it upon himself to state that the Society were aiders
and abettors in the action referred to; and in reply was referred to a
paragraph in the Paisley newspaper of 15th July 1883, in which the
Co-operative Baking Society, Kinning Park, was published as one of
the abettors. Mr Mann had no doubt that the statement was correct,
and warned the Society that it was necessary to attend to his former
letter at once to save future trouble. The Bakery board replied to
threat by threat. If any further communication was received from Mr
Mann, the matter was to be put into the hands of the Society’s law
agent, who was to raise an action against him for trying to extort
money on false pretences, as the Society had never paid any money
to assist in the “Right of Way” case. Nothing more seems to have
been heard of the subject, for nothing further appears in the minutes
regarding it.
In August 1887 the building committee, having completed their
labours, were thanked for their services, and dissolved. The
buildings, plant, and stocks in the new bakery were insured for
£16,000, while the buildings and plant in St James Street were
insured for £2,000. About this time the directors were called on to
consider some grievances under which the employees, and
particularly the vanmen, alleged that they suffered. The first of those
had reference to attendance at the stables on Sundays. The
committee made investigations, and came to the conclusion that no
grievance was suffered. Attendance on Sundays to look after the
comfort of the horses was not work, they decided, but an act of
mercy, which was not paid for anywhere. The other grievance—that
the vanmen by the nature of their work did not get regular holidays
“and had no opportunity of going to the coast with their families”—
the directors thought well founded, and they decided to allow three
consecutive days to each man in future, in addition to the holidays
they at present received; stipulating, however, that no two men were
to be on holiday at the same time.
A NEW VENTURE.
In September, after the new bakery was opened, the Society began
the baking of morning rolls, a branch of trade which immediately
became popular with the members of the societies. For this trade two
light vans and two fast horses were purchased, and the result was
that not only was a large trade in breakfast rolls done, but the bread
trade increased rapidly also. The baking of rolls had, as a matter of
fact, cut the last link which chained some of the societies to the
private baker. The bakers did not surrender the trade of the societies
without a struggle, however. Finding that they were ousted from the
roll trade, they turned their attention to buns as a means of
recapturing the lost trade, and for a time they were successful with a
number of the societies. But the Bakery directors were alive to the
danger, and ere long they also were baking buns at M‘Neil Street.
THE CHAIRMAN RETIRES.
Having seen the new premises in full operation, Mr Fraser came to
the conclusion that the time had come when he should resign his
position as president of the Society. During his seven years of office
he had seen the trade doubled; he had seen the handsome new
bakery erected and opened; and he had seen the Society established
in an unassailable position. While a member of the committee,
during the presidency of Mr Brown, and while he had been
president, he had been a hard worker for the success of the Society,
and well deserved the words of eulogy in which Mr Slater conveyed
the thanks of the committee to him at the last meeting of the board
before his retiral. He was succeeded by Mr John Ferguson, Glasgow
Eastern Society.
Inside a month or two, he was followed into retirement by Mr
Thomas Slater, secretary. Mr Slater had been elected secretary in
1875 when Mr Smith became manager, and had discharged the
duties of his office faithfully and well. At the time of his retiral, and
indeed for many years before then, he had the longest record of
service on the board of the Society. Mr Peter Glasse, St George,
succeeded him.
INCREASES ALL ROUND.
At the end of 1887 the Society was doing a trade of over 410 sacks
per week, and in the first month of the new year 600 new shares
were granted to societies. By the end of the 77th quarter the trade
had risen to 446 sacks per week, and a dividend of 1/3 was paid. The
increases which were taking place in the numbers of shares held by
the societies pointed to increases in membership, and therefore to
opportunities for increased trade by the Federation. The directors
were fully alive to this phase of the subject, and although they were
still a considerable distance from producing the full capacity of the
bakery, it was becoming evident that if the present rate of increase
continued that limit would soon be reached. At the same time they
could be pardoned if they felt that the delegates were not as
appreciative of the work which was being done as they might have
been. This lack of appreciation was shown in a remarkable and
unprecedented manner at the 76th quarterly meeting of the Society
when, by a majority of two votes, it was decided to reduce the
payments made to them for their services from 3/ to 2/ per meeting.
Lack of appreciation could hardly have gone further short of asking
them to resign in a body. It was a very shabby return for the years of
strenuous work which had made the Baking Society that outstanding
instance of Co-operative enterprise which it had become. The
directors went on with their work calmly, however, content to merit,
even if they did not receive, the appreciation to which their efforts for
the success of the Federation entitled them.
CHAPTER IX.
M‘NEIL STREET: RAPID DEVELOPMENTS.
A BISCUIT FACTORY—FURTHER EXTENSIONS—THE U.C.B.S.

AND THE S.C.W.S.—AN ACCIDENT—RESIGNATION OF
FOREMAN BAKER—CO-OPERATIVE FAILURES—THE
MANAGER RESIGNS—FIRST GLASGOW BOYCOTT—A NEW
PRESIDENT—MAJORITY CELEBRATIONS—THE DINNER—
STILL MORE EXTENSIONS—THE INFLUENCE OF
CONGRESS—EXTENSIONS AGAIN—ST JAMES STREET
PREMISES SOLD—NEW BUILDING COLLAPSES—MORE
BUILDING—BUILDING DEPARTMENT STARTED.
The Baking Society had now entered on a period of extraordinary

development. Department was added to department and extension
followed extension with marvellous rapidity. It seemed, indeed, as if
the spirit of Co-operation had only been waiting for a suitable
habitation in order to show the great things of which it was capable.
In the six years—1888–1894—the output of the Society rose from
466 sacks per week to 1,254, and the number of departments in the
bakery from two to seven, while tearooms had been opened, a
purveying department was being carried on, and a workshops and
trades department was in operation. The sales for the 77th quarter
were £12,438; by the end of the year they were £16,490, and by the
88th, which, however, was a fourteen week quarter, they were
£27,210. The trade had more than doubled in three years. In the
same period the membership, which had been thirty-six societies at
the end of the 77th quarter, had grown to forty-six at the end of the
88th.
Before the Society had been six months installed in M‘Neil Street
the committee were beginning to have visions of congestion such as
they had experienced in St James Street, unless they took time by the
forelock and made arrangements which would enable them to
grapple with their ever-increasing trade before it again overwhelmed
them. The first business they decided to tackle was that of erecting a
biscuit factory, where they could produce fancy biscuits of all kinds.
Hitherto they had been getting such biscuits as they were able to sell
from a firm of manufacturers in the city, and were having them
invoiced through the S.C.W.S. Investigation showed that this mode
of procedure was one which was not profitable to the Society, but, at
the time when the investigation was made, the directors were not in
a position to do anything; and when they secured the ground on
which to build their new factory the congestion in their bread
department made instant provision for that department the premier
necessity. But now that they had the bread difficulty settled for a
short time they turned their attention to the question of biscuits.
Provision had been made in the new building for a travelling oven,
but its installation had been held over while the more important
work was being carried out. Early in 1888, however, it was decided to
purchase a biscuit cutting machine, and one similar to the working
model which was being shown in Glasgow Exhibition was ordered, at
a cost of £258. They did not act without caution, however, for before
the machine was purchased they wrote to the manager of Crumpsall
bakery for his opinion of the biscuit machines made by the firm from
which they proposed to purchase. With the object of ensuring that
everything possible would be done to promote the sale of the biscuits
when they were made, the committee also approached the directors
of the Wholesale Society as to the likelihood of that federation
becoming agent for the U.C.B.S. in the biscuit trade. They were
informed that the Wholesale Society viewed the proposal favourably,
and were likely to adopt it when the occasion arose. The societies
were all circularised with the view of ascertaining what was the
aggregate trade in biscuits which might be expected.
FURTHER EXTENSIONS.
Hitherto the committee had only the erection of a biscuit factory in
mind, and plans for that building had been prepared, and in January
of 1889 were considered by them. By February, however, they came
to the decision that a biscuit factory was not enough. The trade now
exceeded 600 sacks per week, an increase of 200 sacks inside the
year, and they were of opinion that further extensions were necessary
to meet the growing demand for bread. They therefore asked the
quarterly meeting for permission to spend between £3,000 and
£4,000 on the erection of a new wing to the bakery. This power was
granted readily.
They were now ready to proceed, but they had learned something
from their experience while the first portion of M‘Neil Street
premises was being erected, so they decided to consult with the
architect as to whether it would be advisable to put the whole of the
work in connection with the erection of the building into the hands of
one contractor, so as to get a time limit inserted in the contract. The
architect, however, was not in favour of placing all the work in the
hands of one contractor. The firm of masons who had built the
earlier section were again successful in obtaining the contract for the
building work. The contracts for the whole of the building work were
fixed for a total sum of £5,532. A few weeks later a contract was fixed
up for the erection of a travelling biscuit oven, at a cost of £200.
The new building when completed added very considerably to the
Society’s productive power. It contained on the first flat the pastry
bakehouse with four ovens; on the second flat the fancy biscuit
department with one travelling oven and four ordinary ovens; the
third flat was devoted to the operations of the biscuit and pastry
packing workers; while on the fourth flat was the new oatcake
bakery. The whole of the new wing was finished and ready to start
operations at the beginning of April 1890, and not before it was
required, for the average output had grown by then to 715 sacks per
week, fifteen sacks more than the first building in M‘Neil Street had
been erected to produce.
THE U.C.B.S. AND THE S.C.W.S.
At the end of 1888 the Wholesale Society had become members of
the Baking Society, and had taken out 240 shares. This was done,
doubtless, in view of the fact that the Wholesale Society had
consented to act as agents for the Baking Society’s biscuits. On the
other hand, the trade which was being done in flour with the
Wholesale Society was far from satisfactory, and at a meeting of the
Baking Society’s committee, which took place in February of 1889,
attention was called by the sub-committee to the fact that, of over
2,000 sacks of flour which had been purchased during the month,
only 300 sacks had been bought from the Wholesale Society. It was
agreed to call the attention of the Wholesale directors to this fact,
and to state that the trade was going past them because their price
was higher than the same flour was being purchased at elsewhere. As
a result of this letter, the Wholesale Society appointed a deputation
to meet with a deputation of the directors of the Baking Society for
the purpose of considering the trading relations between the two
societies. Exactly what the result of the meeting was, however, is not
shown in the minutes; all that these contain being the statement that
Mr M‘Culloch gave a very full report of what had taken place. From
the frequency with which this subject had been cropping up in recent
years, however, it was evident that there was something wrong
somewhere. At this late date it is not possible to do more than guess
at the reasons why the Wholesale Society was not in a position to
compete, but it was probably owing to the fact that the Baking
Society was now so large a purchaser of flour that it was able to buy
from the millers on as good terms as the Wholesale Society itself
could do.
AN ACCIDENT.
Notwithstanding the large number of vehicles which the Society
had on the road, it had been wonderfully free from accidents of a
serious nature. Hitherto the killing of the Tramway Company’s horse
had been the most serious, and the results of that accident had been
serious, not so much because of the accident itself, as because of the
litigation which followed. Early in 1889, however, an accident
occurred on the Albert Bridge, which although, fortunately, not so
serious as it might have been, yet served to impress on the vanmen in
the service of the Society the necessity for caution when driving
through the streets of the city. Two men were run down on the bridge
by one of the Society’s vans and injured, and the vanman was
arrested and fined. The Society agreed to pay the fine, and also
settled with the injured men for £10, but the vanman was dismissed
from the service of the Society.
About this time a petition was again received from the vanmen
with reference to holidays and Sunday labour. The men wished the
three days’ holidays which they were allowed increased to six days,
while they also wished payment for attending to the horses on
Sundays. The committee could not see their way to make any further
concession of holidays, but they agreed that men who had to spend a
full day in the stable on Sundays should receive a day’s pay. This was
probably the first occasion in Glasgow on which it was recognised
that wages paid to vanmen and carters were for a six-day week, and
that work on the seventh day should be paid for. In this matter as in
so many others the Baking Society were pioneers, and it was not until
more than twenty years had passed that the trade union was able to
enforce all over the city the rule that Sunday work in the stables
should be paid for.
RESIGNATION OF FOREMAN BAKER.
At the end of the 79th quarter Mr Lang, who had been foreman
baker with the Society during all the time they had been in St James
Street, resigned his situation, and a Mr Marshall was appointed. Mr
Marshall came to the Society with excellent testimonials, but,
somehow or other, after his appointment the number of complaints
with regard to the quality of the bread increased steadily, and at
times came in from a dozen societies at once. He was interviewed
repeatedly by the committee and the necessity of maintaining a high
standard in bread was impressed on him, but little improvement
took place. At length it was discovered by the sub-committee that he
was absent from work without leave, and he was suspended by them,
and at the next meeting of the full committee was dismissed, and Mr
Robert Fraser was appointed. From Mr Fraser’s appointment
complaints became much less frequent.
There were districts where Co-operation was not yet firmly
established, and through the policy of the directors, which made for
helping societies wherever possible, small sums were still being lost
occasionally. The next society to close its doors was Clippens. For
some time it had been in low water, and as the Federation was
finding it impossible to obtain payment the supply of bread was
stopped. The committee of the Renfrewshire Co-operative
Conference Association undertook, however, to try and get that
association to become security for payment, and supplies were again
granted, but only for a short time as, when the matter came before
the Conference, the delegates refused to accept any responsibility. It
was then arranged that payment should be made for the bread on
delivery, and that payments should be made periodically for the
purpose of reducing the debt of the society. In a very short time this
arrangement also was departed from, and the society shortly
afterwards collapsed, the assets only paying ½ per £ of the debts
owing. There were other societies which were not paying their
accounts regularly, and on several occasions these were written to
and requested to make prompt payments. About this time, also,
Cessnock Society went into liquidation, but were able to pay about
twenty shillings in the pound.
RESIGNATION OF MANAGER.
Mr David Smith had been manager of the Society from the time
when Mr Robert Craig resigned, in the summer of 1875; while prior
to that time he had acted as secretary, and he had been a member of
the committee from the first year of the Society’s existence, having
been the representative of St Rollox Society. He had thus an
unbroken acquaintance with the work of the Society as member of
committee, secretary, and manager for almost twenty years; but the
time had now arrived when he decided to sever his connection, and
so, in October 1889, he intimated to the committee that he was
resigning in order to commence business for himself. His resignation
was accepted, and at the same meeting a special sub-committee was
appointed to make inquiries from the heads of the various
departments with the object of ascertaining whether it was possible
to carry on the business without a general manager. The result of this
inquiry was that the committee decided to rearrange the methods of
business by giving each departmental manager full control of his
department under the committee, thus obviating the necessity of
appointing a general manager in the meantime. Instead of a general
manager it was decided to appoint a cashier and accountant who
should have full control of the office, and Mr James H. Forsyth, from
the accountancy department of the Wholesale Society, was
appointed.
THE FIRST GLASGOW BOYCOTT.
It was in the later years of the ’Eighties that the first Glasgow
boycott took place, and it struggled on spasmodically for several
years. It had very little evil effect on the progress of the Co-operative
movement, but here and there it served to teach the members and
directors of societies a much-needed lesson as to the value of Co-
operative federal institutions. Particularly was this the case with one
society mentioned in the last chapter as receiving exceptional
conditions from private bakers. As a result of the boycott two out of
the three baking firms which had been supplying the society with
bread refused to do so any longer, with the result that the directors
had to appeal to the Federation to come to their rescue. This the
directors of the Federation were quite ready to do, and so the society
joined the Federation and had bread delivered to its members at a
cost of 1/3 per hour, instead of getting it delivered free and being
relieved from responsibility for bad debts, which were the terms
given by the firms which had failed it when the strain came. Another
society which was suffering through the application of the boycott by
the bakers who supplied it was High Blantyre, which also appealed
for assistance, and shortly afterwards became a member of the
Federation. The membership of the city societies was also growing
very rapidly, and this growth was being reflected in the sales of the
Federation, which showed a progressive increase every quarter. At
the beginning of the 78th quarter the number of societies affiliated
was thirty-six; when the coming-of-age celebrations took place two
years later the membership had increased to forty-two societies
notwithstanding that Clippens and Cessnock societies had ceased to
exist.
A NEW PRESIDENT.
Another important change which took place at the end of 1889 was
the retiral from the presidency of Mr John Ferguson and the
appointment of Mr Duncan M‘Culloch in his place. This change
marked the beginning of a period of unexampled expansion in the
growth of the Society. Just about this time, also, the Federation was
asked to supply Dumbarton Society with bread while that society’s
own bakery was being rebuilt. The Federation at the end of this year
was making a big bid for the trade of the societies in cakes and buns
for the New Year trade. They had embarked on this trade on a small
scale some time earlier, but the business done for the season 1889–
1890 was important enough to find a place in the minutes as being
25 per cent. greater than that of the previous year.
MAJORITY CELEBRATIONS.
Early in February 1890, when the new buildings were approaching
completion, it was decided that the opening of these for trade should
also be taken advantage of to celebrate the coming of age of the
Society, and somewhat elaborate provision was made to have a
function which would advertise the business of the Society. It was
agreed that five tickets should be sent to every society doing a trade
of £250, ten tickets to those societies whose trade was between £250
and £500, and fifteen tickets to societies whose trade was over £500.
At a later meeting it was agreed that one bottle of beer be supplied to
each guest attending the celebration.
The celebration of the majority of the Society, combined as it was
with the opening of the new wing of the bakery premises, was a
notable demonstration of the progress of Co-operation. The opening
ceremony was on a grand scale, as in addition to the large number of
delegates who had been invited there were also present a number of
visitors, including some from England. Mr M‘Culloch presided, and
the opening ceremony was performed by Mr Glasse, secretary of the
Society, declaring the premises open in a brilliant speech in which he
traced the history of the Federation from its earliest days, and
commented on the wonderful progress it had made. The occasion, he
said, was one of which the Co-operators of the West of Scotland
should be proud. They were met in buildings which were
magnificent, and which were a fine example of what might be done
by working men. He reminded his audience that only three years had
elapsed since they had met at the same place to open the original
buildings. At that time the committee did not think that an extension
would be required so soon; the only difficulty they had anticipated
being that of finding sufficient trade to keep the bakery fully
occupied. That difficulty was soon overcome, however, and the trade
had increased so rapidly that they were forced to proceed with the
buildings they were met to open that day. How necessary the new
buildings were he illustrated by pointing out that while M‘Neil Street
original bakery had been erected to do a trade of 700 sacks per week,
the quarter which would end on the 27th April would show, he
anticipated, an average output of 715 sacks per week. When they had
started in St James Street it took fourteen years to work up to their
full capacity of 400 sacks per week, but now they had increased their
trade by over 300 sacks a week in rather less than three years. He
hoped that the biscuit factory which they were opening that day
would prove as great a success as the bread baking factory had done,
and that many societies outside the Federation’s radius for bread
would avail themselves of its products. The United Co-operative
Baking Society was one of the grandest examples of Co-operation
which they had in the country, and it was fast becoming one of the
largest producers of bread in the West of Scotland. He referred to the
conditions under which the baking trade was carried on in the small
bakeries, quoting the Lancet as having stated that many of the
workmen had to work under conditions that were abominable, and
he invited those present to walk through the bakery and see that
everything there was clean and sweet. He pointed out that, of the 140
bakeries in Glasgow, three did as much trade as the whole of the
remainder. It was gratifying, he continued, that during the whole
twenty-one years of its existence the Baking Society had not had a
single dispute with its employees. They had always paid the best
wages and employed the best hands. Besides the usual discount, also,
the Society had paid £34,170 as dividend on purchases, and that fact
in itself spoke for the value of the Federation.
Mr Glasse then, by pulling a lever, set the machinery in motion
and declared the premises open.
THE DINNER.
Mr M‘Culloch presided also at the dinner, at which more than 400
guests were present, including Mr Ben Jones. In his address of
welcome the chairman asked the delegates to project their minds
into the future and ask themselves what would be the magnitude of
that branch of the Society’s business which they were starting that
day when they met to celebrate the coming of age of the biscuit
factory twenty-one years hence. He also referred to the fact that all
the presidents of the Society but one were present with them.
Speeches were delivered by Messrs J. Lochhead, Ben Jones,
William Revie, Gabriel Thomson, Donald Cameron (two ex-
presidents), Mr Glasse, Mr J. Ferguson, Mr J. M‘Murran, Mr William
Barclay (another ex-president), and Mr Malcolm Neil. Mr Jones
described London, from which he had come, as “a Co-operative
desert,” while, in proposing “Retail Co-operation,” Mr Glasse said
that in the Second City of the Empire retail Co-operators were nearly
as bad as they were in the first, although during the past five years
some headway had been made in the city.
STILL MORE EXTENSIONS.
The year 1890 was the year in which the Co-operative Congress
was last held in Glasgow. There had been an earlier Congress held in
the city—in 1876—but it passed without much note being taken of it,
and seemingly without having had much influence save on those who
were in close touch with it. It was different with the Congress of
1890, however. It gave an impetus to Co-operation in the city which
was felt by every society, and the effects of which have not died out
even yet. It was like that first strong push which overcomes the
inertia of a snowball at the top of a steep slope, and sends it rolling
down hill, ever increasing in speed and in size as it rolls on. To some
extent the ground had been prepared for the Congress by the
Wholesale Society in its erection of the buildings at Shieldhall; an
evidence of the life of Co-operation in the city which could not fail to
appeal to the imaginations of a commercial people like the
Glaswegians; and by the opening of the new bakery at M‘Neil Street,
and the big Co-operative demonstration which accompanied that
opening. Shieldhall and M‘Neil Street might be likened to the gentle
rain which watered the feeble plant of Co-operation in the city, and
the 1890 Congress to the sun, the warmth of whose rays caused it to
blossom and grow strong.
Co-operation made itself manifest in various ways during Congress
week. The Bakery was thronged with visitors; flags floated gaily from
the tops of the buildings, and a grand Co-operative procession took
place through the city, during which the lifeboat “Co-operator” was
launched on the Clyde. The directors of the Baking Society were not
slow to take advantage of all this enthusiasm for Co-operation. They
took a stall at the Congress Exhibition of Co-operative productions,
and attracted much attention by the high quality of the goods shown.
The result was that the trade of the new biscuit department received
a send off it might not otherwise have secured. Many orders were
booked during the Exhibition week, and others came flowing in for
weeks afterwards.

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Advances in Organometallic Chemistry

Volume 67 Pedro J. Pérez (Eds.)

Advances in Organometallic Chemistry Volume 65 Pedro J.

Advances in Organometallic Chemistry Volume 66 Pedro J.

Advances in Organometallic Chemistry 1st Edition Pedro

Advances in Organometallic Chemistry 66 1st Edition

Advances in Organometallic Chemistry and Catalysis The

Organometallic Chemistry in Industry A Practical

Advances in Quantum Chemistry Ratner Volume John R.

Organometallic chemistry 1st Edition Ian Fairlamb

First edition 2017

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Publisher: Zoe Kruze

To the memory of Prof. Jose Barluenga (1940–2016), a pillar of the foun-

Group 6 Metal Fischer Carbene

Advances in Organometallic Chemistry, Volume 67 # 2017 Elsevier Inc. 1

6.5 Synthesis of Seven- and Eight-Membered Carbocycles 85

Although they have been occasionally proposed as reactive intermediates in

metal-templated reactions are initiated by the dissociation of a carbonyl

2. SYNTHESIS OF GROUP 6 METAL CARBENE

Scheme 1 Common approaches for the synthesis of group 6 metal FCCs.

R3CHO, NEt3 OR2

1) 1 equiv. n-BuLi, −78°C, Et2O

Scheme 3 Synthesis of alkenyl FCCs by condensation with aldehydes.

1) THF, −80°C OR*

1) THF, −80°C 3) −80 to 25°C

of stoichiometric amounts of pregenerated W(CO)5THF (Scheme 6).

3. RELEASE OF THE ORGANIC MOIETY ON FCCs

diazomethane53 or Wittig phosphorus ylides54 or hydrogenation leading to

4. APPLICATIONS OF ALKYL CARBENE COMPLEXES IN

4.1 Synthesis of Acyclic Compounds

Scheme 9 Synthesis of α-amino esters by photolysis of aminocarbene complexes.

Tungsten alkoxy FCCs 52 undergo the nucleophilic attack of zinc-

4.2 Synthesis of Three-Membered Carbocycles

Z R1 OR2 Z OR2 Z OR2

Scheme 14 Synthesis of cyclopropanes by [2+1]-reaction of FCCs and alkenes.

R1 = alkyl (1°, 3°), alkenyl, aryl, TMS

On the other hand, for electron-rich olefins metathesis products 62 are

1) THF, −78 to 20°C

yields are increased when cyclopropanol decomposition during purification

R1 = alkyl, alkenyl, aryl R2 O

The cyclopropanation reaction is rather elusive for amino FCCs, espe-

cyclopropylpyrroles 80 in moderate to good yields and with low dia-

4.3 Synthesis of Four-Membered Carbocycles

NR22 111°C, toluene R3

Scheme 21 Synthesis of cyclobutanones from FCCs and olefins.

the employment of cyclic conjugated dienes, such as cyclohexadiene, or of

Usually chromium methoxy FCCs 9 react thermally with silyl-

4.4 Synthesis of Five-Membered Carbocycles

Scheme 24 Reaction conditions and mechanism for the synthesis of cyclopentenones.

been found to be an intermediate for this reaction.95 Then, a cyclopropane

A BISCUIT FACTORY—FURTHER EXTENSIONS—THE U.C.B.S.

The Baking Society had now entered on a period of extraordinary

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To the memory of Prof. Jose Barluenga (1940–2016), a pillar of the foun-