The first general enantioselective catalytic Diels-Alder reaction with simple α,β-unsaturated ketones
The first general enantioselective catalytic Diels-Alder reaction with simple α,β-unsaturated ketones
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DOI：
10.1021/ja017641u
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发表时间：
2002-03-20
影响因子：
15
通讯作者：
MacMillan, DWC
中科院分区：
文献类型：
--
作者：
Northrup, AB;MacMillan, DWC
第一个通用方法Diels - Alder反应的对映选择性催化与简单的二亲酮已经完成。使用铝催化使得对映选择性获得了Diels - Alder反应的基本变体，而以前使用手性Lewis酸催化是无法获得的。开发了一种新的手性胺催化剂，使多种单齿环酮和无环酮成功参与对映选择性[4 + 2]环加成。广泛的环状和非环状二烯底物也可以在这种新的有机催化转化中适应。提供了一个计算模型，该模型符合在本研究过程中所观察到的所有反应的对映体诱导意义。
The first general approach to enantioselective catalysis of the Diels−Alder reaction with simple ketone dienophiles has been accomplished. The use of iminium catalysis has enabled enantioselective access to a fundamental Diels−Alder reaction variant that has previously been unavailable using chiral Lewis acid catalysis. A new chiral amine catalyst has been developed that allows a variety of monodentate cyclic and acyclic ketones to successfully participate in enantioselective [4 + 2] cycloadditions. A wide spectrum of cyclic and acyclic diene substrates can also be accommodated in this new organocatalytic transformation. A computational model is provided that is in accord with the sense of enantioinduction observed for all reactions conducted during the course of this study.