Theoretical rationale for regioselection in phosphine-catalyzed allenoate additions to acrylates, imines, and aldehydes

被引:139
作者
Dudding, Travis [1 ]
Kwon, Ohyun
Mercier, Evan
机构
[1] Brock Univ, Dept Chem, St Catharines, ON LS2 3A1, Canada
[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
关键词
D O I
10.1021/ol061095y
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A rationale for regioselection in phosphine-promoted annulations of acrylates, imines, and aldehydes with allenoates has been developed using computation at the B3LYP/6-31G(d) level of theory. The computed transition states revealed that Lewis acid activation, strong hydrogen bonding (H-bonding), and minimization of unfavorable van der Waals contacts are the guiding factors responsible for regioselection. An excellent level of correlation between the calculated regioselectivities and experiment was observed.
引用
收藏
页码:3643 / 3646
页数:4
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