Enantioselective cyanosilylation of ketones by a catalytic double-activation method with an aluminium complex and an N-oxide

被引:99
作者
Chen, FX
Zhou, H
Liu, XH
Qin, B
Feng, XM [1 ]
Zhang, GL
Jiang, YZ
机构
[1] Sichuan Univ, Coll Chem, Minist Educ, Key Lab Green Chem & Technol, Chengdu 610064, Peoples R China
[2] Chinese Acad Sci, Chengdu Inst Biol, Chengdu 610041, Peoples R China
[3] Chinese Acad Sci, Chengdu Inst Organ Chem, Chengdu 610041, Peoples R China
关键词
asymmetric catalysis; cyanohydrins; double activation; enantioselectivity; ketones;
D O I
10.1002/chem.200400506
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Double-activation catalysis promises high catalytic efficiency in the enantioselective cyanosilylation of ketones through the combined use of a Lewis acid and a Lewis base. Catalyst systems composed of a chiral salen-A1 complex and an N-oxide have high catalytic turnovers (200 for aromatic ketones, 1000 for aliphatic ones). With these catalysts, a wide range of aliphatic and aromatic ketones were converted under mild conditions into tertiary cyanohydrin O-TMS ethers in excellent yields and with high enantioselectivities (94% ee for aromatic ketones, 90% ee for aliphatic ones). Preliminary mechanistic studies revealed that the salen-A1 complex played the role of a Lewis acid to activate the ketone and the N-oxide that of a Lewis base to activate TMSCN; that is, double activation.
引用
收藏
页码:4790 / 4797
页数:8
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