铑催化不对称氢化2-苯基-2-丙烯醇合成手性2-苯基丙醇.pdf

第31卷第11期
应用化学
2014年11月
CHINESE JOURNAL OF APPLIED CHEMISTRY
Nov.2014
研究简报
Enantioselective Synthesis of Chiral 2- Phenylpropanol
via Rh-catalyzed Asymmetric Hydrogenation
of 2-phenylprop-2-en-1-ol
DUAN Zhengchao"", WANG Lianzhi", QU Taoli, ZUO Xiaoyu", HU Xiangping", ZHENG Zhuo
(School of Chemical and Enironmental Engineering, Hubei University for Nationalities, Enshi 445000, China
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Abstract Rhodium-catalyzed asymmetric hydrogenation of 2-phenylprop-2-en-1-ol was investigated for the first time
Enantioselective synthesis of chiral 2-phenylpropanol with up to 70% ee was achieved through screen on a series of
monodentate ligands and bidentate ligands
Keywords chiral phenylpropanol, Rh(I) complex, asymmetric catalytic hydrogenation, phenylprop-en-ol, chiral
phosphorus ligand
CLC number. 0621
Document code. A
Article ID:1000-0518(2014)11-1356-03
DOI:10.3724/SP.J.1095.2014.40054
Derivatives of chiral 2-phenylpropanol are frequently used as components of fragrance mixtures(for
example, commercial odorants Muguesia and Pamplefleur and also as intermediates for the synthesis of
naturall products and drugs The methods for synthesizing optically active 2-phenylpropanol include the
resolution of alcohol racemates by lipase-catalyzed transesterification enantioselective methylalumination of
terminal alken(3:, enantioselective hydroformylation of styre e 44) Catalytic asymmetric hydrogenation of the
corresponding prostereogenic 2-phenylprop-2-en-1-ol should be one of the most effective methods for the
construction of this molecule because of its inherent efficiency and atom economy]. Although sigr
progress has been made in the catalytic asymmetric hydrogenation of 2-phenylprop-2-en-1-ol with various In
complexes, Rh complex applied in this reaction remains unexplored. Herein we report for the first time an
enantioselective rhodium-catalyzed hydrogenation of 2-phenylprop-2-en-i-ol, and chiral 2-phenylpropanol was
prepared in good enantioselectivity under mild reaction conditions
Initially, some commercial ligands were applied in the Rh-catalyzed asymmetric hydrogenation of
2-phenylprop-2-en-l-ol. The results were summarized in Table 1
Most of the bidentate phosphorus ligands proven to be successful for the highly enantioselective
hydrogenation of various olefins gave unsatisfactory results in this transformation(Table 1). For example
DUPHOS showed low activity under the reaction conditions(entry I Bophoz, Taniaphos and Walphos were
effective for this hydrogenation, however, the enantioselectivity was very low(entries 2.4). BINAP can give
moderate enantioselectivity and complete conversion(entry 5). Some monodentate ligands(Fig.1 ) were
applied in the hydrogenation, however, the results were not satisfied(entries 6-8)
Recently, some ligands were developed in our laboratory, which showed high reactivity and selectivity in
Reveived 2014-02-25; Revised 2014-05-07; Accepted 2014-06-16
Supported by the National Natural Science Foundation of China(No. 21262011)
Corespondingauthor:DUANZhengcha,asscaeprofessor;Te/Fax0718-84353;E-mail:dzhch168@163.com;ResearchInterests
asymmetic synthesis
Co-corresponding author: HU Xiangping, professor; Tel: 0411-84379