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To cite this article: Jiayun Li , Jiajian Peng , Ying Bai , Lingzhen Chen & Guoqiao Lai (2011)
Rapid Selective Defunctionalization of the Carbonyl Group of ,-Unsaturated Ketones with
Trialkoxylsilane/ZnX2 , Phosphorus, Sulfur, and Silicon and the Related Elements, 186:8, 1621-1625,
DOI: 10.1080/10426507.2010.536188
To link to this article: http://dx.doi.org/10.1080/10426507.2010.536188
Abstract Reduction of the carbonyl group of ketones to a methylene unit is widely applied in
organic syntheses. In this article, we report that trialkoxylsilane/Zn-based catalyst systems may
be applied in the reduction of the carbonyl groups of ,-unsaturated ketones to methylene
units under very mild conditions. In comparison with other Zn-based catalysts, excellent
rates and high conversions of ,-unsaturated ketones to methylene units are obtained using
trialkoxylsilane/ZnI2 or ZnCl2 . And the same time, the hydrosilylation reaction product could
only be detected when using CuI, CuCl, or FeCl3 . No reaction could be conducted by using
trialkoxylsilane/CoCl2 or NiCl2 , in comparison with Zn-based catalysts.
Supplemental materials are available for this article. Go to the publishers online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Defunctionalization of carbonyl group; trialkoxylsilane/ZnX2 ; ,-unsaturated
ketone
INTRODUCTION
Reduction of the carbonyl group of ketones to a methylene unit is widely applied in
organic syntheses.1 However, only a few protocols for the defunctionalization of a carbonyl
group to a methylene group have been reported. These include the Clemmensen reduction,2
WolffKishner reduction, and WolffKishnerHuang reduction,3 all of which require
Received 26 August 2010; accepted 27 October 2010.
We are grateful to the Fund of Zhejiang province (2008C14041) and Technologies R&D Program of
Hangzhou city (20100331T16) for financial support.
Address correspondence to Jiajian Peng and Guoqiao Lai, Key Laboratory of Organosilicon Chemistry
and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, Peoples
Republic of China. E-mail: jjpeng@hznu.edu.cn; gqlai@hznu.edu.cn
1621
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J. Li ET AL.
rather drastic reaction conditions. Other methods, including catalytic hydrogenation,4 reduction with trialkylsilanes/trifluoroacetic acid5 or trichlorosilane/trialkylamine6, and metal
hydride reductions,7 have been successfully applied more specifically to aryl aldehydes and
ketones. Recently, Chandrasekhar et al.8 reported the polymethylhydrosiloxane/B(C6 F5 )3
combination to be a versatile carbonyl defunctionalization system. In this article, we report
that trialkoxylsilane/ZnX2 systems may be applied in the reduction of the carbonyl groups
of ,-unsaturated ketones to methylene units under very mild conditions.
In order to investigate the scope and limitation of the trialkoxylsilane/zinc halidecatalyzed reduction of the carbonyl group of ,-unsaturated ketones to a methylene
unit, reactions of other ,-unsaturated ketones were tested. As substrates, we chose
4-phenylbut-3-en-2-one, 4-(4-nitrophenyl)but-3-en-2-one, 1,3-bis(4-nitrophenyl)prop-2en-1-one, 1-phenyl-3-p-tolylprop-2-en-1-one,3-(4-nitrophenyl)-1-phenylprop-2-en-1-one,
3-(4-bromophenyl)-1-phenylprop-2-en-1-one,
3-(4-nitrophenyl)-1-p-tolylprop-2-en-1one, and 1,5-diphenylpenta-1,4-dien-3-one (Scheme 2). Though excellent conversions
were obtained with trimethoxysilane, two reduced isomers involving double-bond transfer
were observed, the isomer distributions of which were controlled by the nature of the
substituent on the phenyl ring (Table 2).
1623
Entry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Silane
Catalyst
Time (h)
Conv. (%)
ZnF2
ZnCl2
ZnI2
Zn3 [Fe(CN)6 ]2
Zn(CF3 CO3 )2
Zn[OOCCH(C2 H5 )C4 H9 ]2
ZnI2
ZnI2
ZnI2
CuI
CuCl
FeCl3
CoCl2
NiCl2
17 min
5 min
5 min
2
6
2
5 min
12
12
2
2
15 min
6
6
46
100
100
100
62.0
72
100
6.2
1.5
98.0
96.8
100
100
100
100
100
100
35.5
100
100
100
64.5
100
100
100
Reaction conditions: r.t.; (E)-chalcone 5 mmol; hydrosiloxane 10 mmol; catalyst: 3 mol% based on (E)chalcone. 3: (E)-1,3-diphenylprop-1-ene; 2: (E)-(1,3-diphenylallyl)trimethoxysilane.
Select. (%)
R1
R2
Conv. (%)
Phenyl
4-Nitrophenyl
4-Nitrophenyl
p-Tolyl
4-Nitrophenyl
4-Bromophenyl
4-Nitrophenyl
Phenyl
Methyl
Methyl
4-Nitrophenyl
Phenyl
Phenyl
Phenyl
P-Tolyl
1-Styryl
100
100
100
100
100
100
100
100
100
100
100
45.0
71.4
85.2
89.8
55.0
28.6
14.8
10.2
100
Reaction conditions: r.t.; ,-unsaturated ketone 5 mmol, HSi(OMe)3 10 mmol, ZnCl2 3 mol% based on
,-unsaturated ketone, 1 h. 4:
; 5:
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J. Li ET AL.
place, generating an active zinc hydride species. This forms an adduct with the carbonyl
of the substrate, thereby forming intermediate state (3) in the first step. Intermediate state
(3) is then converted into intermediate state (5). Hydride attack on the activated carbonyl
of (3) gives a reduced intermediate state (10), from which the hydrosilylation product is
formed. However, the attack of R3 SiH on the activated carbonyl double bond of (5) leads
to intermediate state (6), from which defunctionalized carbonyl to methylene products are
formed. Two reduced isomers involving double-bond transfer were observed in the study.
CONCLUSION
In summary, zinc-catalyzed reduction of the carbonyl group of ,-unsaturated ketones to a methylene unit with trialkoxysilane proceeds smoothly under mild conditions. In
comparison with other Zn-based catalysts, excellent rates and high conversions are obtained
with ZnI2 or ZnCl2 .
EXPERIMENTAL
All substances were purchased from Aldrich and were used as received. Other information is as follows: Gas chromatography (GC): TRACE DSQ GC; column DB-5 30 m
2.5 mm 0.25 m; split 50:1; flow rate 1 mL/min constant flow; inlet temperature 260 C;
column temperature 50 C for 1 min then 15 C/min increase to 260 C (held for 10 min).
1
H NMR spectra were measured using a Bruker AV 400 MHz spectrometer operating
at 400.13. Chemical shifts for 1H spectra were recorded (in ppm) relative to the residual
proton of CDCl3 . 1H NMR 7.24.
1625
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