Journal of the Chinese Chemical Society, 2002, 49, 505-508 505

Low-valent Ruthenium Induced Simultaneous Reduction of Nitro Group

and C-C Double Bond in Nitroolefin 1-Phenyl-2-nitropropene-1

Yanjun Li* ( ) and Taeko Izumi ( )

Department of Chemistry and Chemical Engineering, Faculty of Engineering, Yamagata University,
3-16 Jonan 4-Chome, Yonezawa, 992-8510, Japan

The reduction of 1-phenyl-2-nitropropene-1 (1) on using ruthenium complexes was studied in detail in
or der to cor re late this method with those pre vi ously re corded in the lit er a ture for the hydro ge na tion of
nitroolefins. A variety of products was isolated by varying the reaction temperature and solvent. Among them
was 1-phenyl-2-propylamine (4), completely reduced from the selective both double bond and nitro group.
1-Phenyl-2-propanol (5) was observed due to reduction of phenylacetone at 125 C in the presence of ruthe-
nium cat a lyst. When re ac tion tem per a ture was lower than 125 C, by em ploy ing RuCl 2 (PPh3) 3 com plex,
1-phenyl-2-nitropropane (2) and phenylacetone (3) were obtained, respectively. Ru-BINAP complexes were
attempted to produce chiral amine from starting material 1-phenyl-2-nitropropene-1 (1).

INTRODUCTION kg/cm2); the temperature of the reaction was from room tem-
perature to 100 C (Scheme I). These reactions demonstrated
The reduction of nitro compounds is an important and that the reduction was stepwise and capable of regulation in
widely used transformation in organic synthesis. 1 Complete order to afford the nitroparaffin and ketone in various mix-
reduction providing amines in the case of nitroarenes using tures.
molecular hydrogen in the presence of a catalytic amount of
RuCl2(PPh3)3 was reported by Knifton.2 Reverse addition of Scheme I
lithium alumi num hy dride to nitroolefins demonstrated the Scheme 1
reduction was stepwise and capable of regulation so as to af- NO2
Ru. * NO2 Me
ford the amine, hydroxylamine de riv a tive, oxime or nitro- + O
Me CH2Cl2 Me
paraffin in various mixtures. 3 It is also known that a Pd/C cat-
1 2 3
alyst is efficient in converting nitroolefins to provide corre-
sponding amines finally.4 Herein we focus on asymmetric hy-
The variation of hydrogenation with temperature is pre-
dro ge na tion of nitroolefin com pound 1-phenyl-2- nitro pro-
sented in Fig. 1. When the reaction was performed at room
pene-1 (1) by using ruthenium complexes due to a number of
ho mog e nous and het er o ge neous ru the nium com plexes that
catalyze hydrogenation of various substrates including ole-
fins, aldehydes, ketones and nitro compounds.5,6 The hydro-
genation of 1-phenyl-2-nitropropene-1 was carried out with
RuCl2(PPh3)3 and then stereoselective reactions were investi-
gated by us ing Ru-BINAP com plexes. To our best knowl-
edge, there has been no report in the literature on the asym-
met ric hy dro ge na tion of nitroolefin with these kinds of re-
agents.

RESULTS AND DISCUSSION

Fig. 1. Effect of temperature on re duction of 1-phen -
yl- 2-nitropropene-1 w, yield of 1-phenyl-2-
The ex per i ments were car ried out on re duc tion of 1- nitropropane (2); n, yield of phenylacetone (3);
phenyl-2-nitropropene-1 with CH 2 Cl 2 as sol vent by us ing 5, for ma tion of 1-phenyl-2-propylamine (4);
RuCl 2 (PPh3 ) 3 com plex in the pres ence of hy dro gen (20 =, 1-phenyl-2-propanol (5).
506 J. Chin. Chem. Soc., Vol. 49, No. 4, 2002 Li and Izumi

tem per a ture, the prod ucts 1-phenyl-2-nitropropane (2) and nium com plex (S)-7 was used in this case, 41% of start ing
phenylacetone (3) were ob tained in al most the same yield; material was recovered, then 2 was isolated in 4% ee and 34%
however increasing the temperature to more than 35 C af- yield (Entry 3).
forded a 25-30% yield of 2 and 65-72% yield of 3.
When the hydrogenation of 1-phenyl-2-nitropropene-1
Ph2 O Ph2 H
(1) was car ried out un der 125 °C and 150 °C by us ing P O P P
Ru Ru
RuCl2(PPh3)3 as a cat alyst, it was converted to 1-phenyl-2- P O P P
Ph2 O Ph2 H
pro pylamine (4) and 1-phenyl-2-propanol (5) in about 28-
32% and 65-62% yield, respectively (Scheme II).
(S)-6 (S)-7
Scheme II
Scheme 2
Ph2 Cl
NO2 NH2 Me P P
Ru. * Ru
Me Toluene
+ OH P P
Me
Ph2 H
1 4 5 P P = BINAP

Therefore it showed that reaction temperature was evi-
dently the main ele ment lead ing to control prod ucts. Es pe-
cially 125 °C was available to conduct transformation from
nitro to amine and carbonyl to hydroxyl. It is known that car-
bonyl can be easily hydrogenated to alcohol with ruthenium
catalyzed in the presence of hydrogen. 7 On the basis of this,
phenylacetone (3) might be hy dro ge nated to 1-phenyl-2-
propanol (5) in the process of the reaction. The conversions
of reductions were almost 100% except that the starting mate-
rial was recovered in 30% under room temperature.
Since racemic 1-phenyl-2-nitropropane (2) and 1-phenyl-
2-propylamine (4) have been synthesized using RuCl2(PPh3)3
un der 80 °C and 125 °C, re spec tively, we tried to pre pare
chiral nitroparaffin and amine by using asymmetric reduction
in the presence of chiral ruthenium complexes. Ru(AcO)2[(S)-
BINAP] 8 (S)-6, RuH 2 [(S)-BINAP] 2 (S)-7 and RuHCl[(S)-
BINAP]29 (S)-8 were investigated, and the results are shown
in Table 1. Compared with THF (Entry 1), CH2Cl2 afforded
100% conversion, though 1-phenyl-2-nitropropane (2) was
formed in 10% ee and in 30% yield (Entry 2). When the ruthe-
(S)-8
When the tem per a ture of re duc tion was up to 125 °C
(Table 2), nitro compound 2 and phenylacetone (3) were con-
verted into amine 4 and al co hol 5, with Ru(AcO) 2 [(S)-
BINAP] employed as catalyst and with the reaction tempera-
ture of 160 °C, 1 afforded the amine 4 in 4% ee and in 45%
yield (Entry 6). When the temperature was down to 125 °C,
1-phenyl-2-propylamine (4) was ob tained in 10% ee and in
55% yield (Entry 5). There was almost the same result as in
Entry 5 when the reaction was carried out using RuHCl[(S)-
BINAP]2 complex (Entry 4). All the reactions afforded racemic
1-phenyl-2-propanol (5).
Al though the gen eral mech a nism of hy dro ge nated
nitroolefin known as the first step is described as eq. 1, but
from intermediate 1a the detailed asymmetric hydrogenation
mechanism remains unknown, it is clear that the chiral ligand
BINAP can make the reaction enantioselective. In addition,
nitroolefin compounds can easily perform acidic hydrolysis
to produce corresponding ketone compound via a modified
Nef reaction.10 In order to decrease the yield of ketone and

Table 1. Asymmetric Reduction of (1) on Using Chiral Ruthenium Complexesa

Temp. 2 3
Entry Catalyst Solvent
b c
( C) Yield % ee % Yield %b
1 (S)-6 THF 50 7 0 8
2 (S)-6 CH2Cl2 80 30 10 66
3 (S)-7 CH2Cl2 80 34 4 22
a
The reaction was carried out in the autoclave under 20 kg/cm2 hydrogen pressure for 24 h by
using 1 mol% of ruthenium complex.
b
Isolated yield.
c
Enantiomeric excesses were determined by HPLC analysis using a Chiralcel OD column.
Ruthenium Induced Simultaneous Reduction of 1-Phenyl-2-nitropropene-1 J. Chin. Chem. Soc., Vol. 49, No. 4, 2002 507

Table 2. Asymmetric Hydrogenation of (1) by Using Ruthenium Complexa

Temp. 4 5
Entry Catalyst
( C) Yield %b ee %c Yield %b ee %
4 (S)-8 125 51 4 45 0
5 (S)-6 125 55 10 43 0
6 (S)-6 160 45 4 52 0
a
The reaction was performed in the autoclave with toluene as solvent under 20 kg/cm2
hydrogen pressure for 24 h by using 1 mol% of ruthenium complex.
b
Isolated yield.
c
E.e. was determined by HPLC analysis by using a Chiralcel OD column.

improve amine, the investigation on the application of an ad-
ditive in asymmetric reaction is ongoing in our laboratory.
O
NO2 N
OH eq. 1
Me Me
1 1a
In con clu sion, we have de vel oped a pro to col for the
syn the sis of 1-phenyl-2-nitropropane and 1-phenyl-2- pro-
pylamine based on ruthenium complex catalyzed asymmetric
re duc tion, al though enantiomeric ex cesses were too low.
However, the working catalyst system is limited in reducing
the ni tro group to amine since the re ac tion tem per a ture is
more than 125 °C, and it will have an effect on using ruthe-
nium complexes to prepare chiral amine from nitroolefin.
EXPERIMENTAL SECTION
General Methods
All ruthenium complexes were pre pared ac cording to
the literature procedures. The solvents were purified by short
path distillation. Melting points were determined on a Micro
cap il lary melt ing point ap pa ra tus and are un cor rected. 1 H
NMR was recorded on Varian 500 MHz spectrometer. Flash
chromatography was carried out with silica gel 60 N (spheri-
cal, neutral) from Merck. Enantiomeric excesses were deter-
mined by HPLC analysis using a Chiralcel OD column. All
re ac tions were run in an au to clave un der hy dro gen (20 kg/
cm2).
Procedure in Reduction of 1-Phenyl-2-nitropropene-1 (1)
1-phenyl-2-nitropropene-1 (1) and ruthenium complex
(1 mol%) and solvent 35 mL were added to an autoclave, with
20 kg/cm2 hydrogen pressure, under corresponding tempera-
ture stirring for 24 h. After removal of the solvent, the residue
was purified by column chromatography on silica gel 60 N
(neu tral; hexane-ethyl ac etate, 4 : 1, v/v). 2-nitro-1-phenyl
propane (2) was obtained as a colorless oil. 1H NMR (CDCl3,
500 MHz ) 1.54 (d, 3H, J = 6.7, CH3), 2.99 (dd, 1H, J = 13.8
and 6.9, CH2), 3.31 (dd, 1H, J = 13.8 and 7.3, CH 2), 4.76 (sex,
1H, J = ca. 7.0, CHNO 2), 7.20 (m, 5H, C6H5). b.p. 103-104
°C/4 mm. 1-phenyl-2-propanone (3) was obtained as a color-
less oil. 1H NMR (CDCl 3, 500 MHz ) 2.16 (s, 3H, CH3), 3.70
(s, 2H, CH2), 7.27 (m, 5H, C 6H5). b.p.100 °C/14 mm.
1-Phenyl-2-propylamine (4)
1-phenyl-2-nitropropene-1 (1) and ruthenium complex
(1 mol%) and solvent 35 mL were added to an autoclave, with
20 kg/cm2 hydrogen pressure, under corresponding tempera-
ture stirring for 24 h. When the reactor was cooled to room
tem per a ture and the sol vent was evap o rated, and then 1 M
HCl was added to the residue, the organic layer could afford
1-phenyl-2-propanol (5). The aqueous layer was neutralized
with NH4OH and extracted with ether, the organic layer was
then dried by Na2SO4 and evaporated to light brown 1-phen-
yl-2-propylamine (4) 1H NMR (CDCl3, 500 MHz ) 1.12 (d,
3H, J = 6.9, CH 3), 2.50 (dd, 1H, J = 21.9 and 10.4, CH2), 2.70
(dd, 1H, J = 20.2 and 4.6, CH 2 ), 3.16 (sex, 1H, J = ca. 9.2,
CHNO2), 7.25 (m, 5H, C 6H5). b.p. 102 °C/16 mm.
1-Phenyl-2-propanol (5)
1
H NMR (CDCl 3 , 500 MHz ) 1.25 (d, 3H, J = 14.8,
CH3), 1.56 (s, 1H, OH), 2.76 (m, 2H, CH 2), 4.02 (sex, 1H, J =
ca 20.5, CHOH), 7.26 (m, 5H, C6H5). b.p. 125 °C/25 mm.
ACKNOWLEDGEMENT
We gratefully acknowledge Dr. Abd EL-Wareth Sarhan
for his advice and Mr. Satoshi Murakami for his outstanding
as sis tance with sam ple prep a ra tion and valu able anal y sis
508 J. Chin. Chem. Soc., Vol. 49, No. 4, 2002
work.
Received January 15, 2002.
Key Words
Reduction; Nitroolefin; Chiral amine; Ruthenium
complex.
REFERENCES
1. (a) Kabalka, G. W.; Varma, R. S. In Comprehensive Organic
Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press:
Oxford, 1991, Vol. 8, pp 363-379. (b) Seebach, D.; Colvin, E.
W.; Lehr, F.; Weller, T. Chimia 1979, 31, 1-18.
2. Knifton, J. F. J. Org. Chem. 1976, 41, 1200.
3. Gilsdorf, R. T.; Nord, F. F. J. Am. Chem. Soc. 1952, 74, 1837.
4. (a) Warren, D. M.; Ernst, S. E. Jr.; Sal vador, U. J. J. Am.
Chem. Soc. 1946, 68, 1866. (b) Wagner, D. P.; Rachlin, A. I.;
Teitel, S. Synth. Commun. 1971, 1, 47. (c) Brossi, A.; Van
Burik, J.; Teitel, S. Helv, Chim. Acta. 1968, 51, 1978.
5. Siegel, S. Encyclopedia of Reagents for Organic Synthesis;
Paquette, L. A., Ed.; John Wiley & Sons: Chichester, 1996;
Li and Izumi
Vol. 6, p 4410.
6. (a) Bennett, M. A.; Mathe son, T. W. In Com pre hen sive
Organo-metallic Chemistry; Wilkinson, G., Stone, F. G. A.,
Abel, E. W., Eds.; Pergamon Press: Oxford, 1982; Vol. 4, p
931. (b) James, B. R. Homogeneous Hydrogenation; Wiley:
New York, 1973. (c) Freifelder, M. Practical Catalytic Hy-
drogenation; Wiley-Interscience: New York, 1971.
7. (a) Kitamura, M.; Ohkuma, T.; Inoue, S.; Sayo, N.;
Kumobayashi, H.; Akutagawa, S.; Ohta, T.; Takaya, H.;
Noyori, R. J. Am. Chem. Soc. 1988, 110, 629. (b) Buser,
H.-P.; Spindler, F. Tetrahedron. Asymmetry 1993, 4, 2451.
8. Ohta, T.; Takaya, H.; Noyori, R. Inorg. Chem. 1988, 27, 566.
9. Miyashita, A.; Takaya, H.; Souchi, T.; Noyori, R. Tetrahe-
dron Lett. 1984, 40, 1245.
10. Hass, H. B.; Riley, E. F. Chem. Revs. 1943, 32, 399.
11. The prep a ra tion of start ing ma te rial 1-phenyl-2- nitro pro-
pene-1 (1): A solution of benzaldehyde 6.4 g and ammonium
acetate 1.0 g in nitroethane 20 mL was heated to reflux for 5
h. On cooling, after removal of the solvent, the residue was
purified by column chromatography on silica gel 60 N (neu-
tral; hex ane-chloroform, 2 : 1, v/v), then recrystallized by
hexane and gave 1 as a light yellow crystal 6.2 g (63%), m.p.
71-73 °C. 1H NMR (CDCl3, 500 MHz ) 2.46 (s, 3H, CH 3),
7.43 (m, 5H, C 6H5), 8.10 (s, 1H, CH).