Mechanistic Rationalization of Organocatalyzed Conjugate Addition of Linear Aldehydes to Nitro-olefins
Mechanistic Rationalization of Organocatalyzed Conjugate Addition of Linear Aldehydes to Nitro-olefins
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DOI：
10.1021/ja203660r
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发表时间：
2011-06-15
影响因子：
15
通讯作者：
Blackmond, Donna G.
中科院分区：
文献类型：
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作者：
Bures, Jordi;Armstrong, Alan;Blackmond, Donna G.
对二芳基丙氨醇醚催化丙醛与硝基苯乙烯共轭加成反应的动力学研究表明，产物亚胺物种的形成是速率控制的，反应产物和酸性添加剂都促进了产物的生成。强调了主要的环丁烷中间体在保持高立体选择性方面的有益作用。这种对机理的理解导致了高效反应方案的设计。
Kinetic studies of the conjugate addition of propanal to nitrostyrene catalyzed by diarylprolinol ethers reveal that formation of the product iminium species is rate-determining and is promoted by both the reaction product and acid additives. The beneficial role of a dominant cyclobutane intermediate in maintaining high stereoselectivity is highlighted. This mechanistic understanding led to the design of highly productive reaction protocols.