Curtin-Hammett Paradigm for Stereocontrol in Organocatalysis by Diarylprolinol Ether Catalysts

被引:118
作者
Bures, Jordi [1 ]
Armstrong, Alan [2 ]
Blackmond, Donna G. [1 ,2 ]
机构
[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA
[2] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AZ, England
基金
英国工程与自然科学研究理事会;
关键词
CONJUGATE ADDITION; ALPHA-CHLORINATION; TRANSITION-STATES; MICHAEL ADDITIONS; ALDEHYDES; MECHANISM; REACTIVITY; ENAMINES; ALKENES;
D O I
10.1021/ja300415t
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Detailed mechanistic study of two reactions catalyzed by diarylprolinol ether catalysts, the conjugate addition of aldehydes to nitro-olefins and the alpha-chlorination of aldehydes, leads to the proposal that the stereochemical outcome in these cases is not determined by the transition state of the step in which the stereogenic center is formed from enamine attack on the electrophile but instead is correlated with the relative stability and reactivity of diastereomeric intermediates downstream in the catalytic cycle. This combination of kinetic and thermodynamic factors illustrates a remarkable Curtin-Hammett scenario that can result in either an enhancement or an erosion of the selectivity that would be predicted by the transition state for enamine attack on the electrophile. Evidence is offered to suggest that this concept may represent a general phenomenon for pyrrolidine-based catalysts lacking an acidic directing proton. Implications for catalyst and reaction design are discussed.
引用
收藏
页码:6741 / 6750
页数:10
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