Chiral phosphine lewis bases catalyzed asymmetric aza-Baylis-Hiliman reaction of N-sulfonated imines with activated olefins

被引:327
作者
Shi, M [1 ]
Chen, LH [1 ]
Li, CQ [1 ]
机构
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organomet Chem, Shanghai 200032, Peoples R China
关键词
D O I
10.1021/ja0447255
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In the aza-Baylis-Hillman reaction of N-sulfonated imines (N-arylmethylidene-4-methylbenzenesulfonamides and others) with methyl vinyl ketone, ethyl vinyl ketone, and acrolein, we found that, in the presence of a catalytic amount of chiral phosphine Lewis base such as (R)-2'-diphenylphosphanyl[1, 1']binaphthalenyl-2-ol LB1 (10 mol %) and molecular sieve 4A, the corresponding aza-Baylis-Hillman adducts could be obtained in good yields with good to high ee (70-95% ee) at low temperature (similar to-30 to -20 degrees C) or at room temperature in THF, respectively. In CH2Cl2 upon heating at 40 degrees C, the aza-Baylis-Hillman reaction of N-sulfonated imines with phenyl acrylate or naphthyl acrylate gave the adducts in good to high yields (60-97%) with moderate ee (52-77%). The mechanistic insight has been investigated by P-31 and H-1 NMR spectroscopic measurements. The key enolate intermediate, which has been stabilized by intramolecular hydrogen bonding, has been observed by P-31 and H-1 NMR spectroscopy. An effective bifunctional Lewis base and Bronsted acid phosphine Lewis base system has been disclosed in this catalytic, asymmetric aza-Baylis-Hillman reaction.
引用
收藏
页码:3790 / 3800
页数:11
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