The enantioselective organocatalytic 1,4-addition of electron-rich benzenes to α,β-unsaturated aldehydes
The enantioselective organocatalytic 1,4-addition of electron-rich benzenes to α,β-unsaturated aldehydes
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DOI：
10.1021/ja025981p
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发表时间：
2002-07-10
影响因子：
15
通讯作者：
MacMillan, DWC
中科院分区：
文献类型：
--
作者：
Paras, NA;MacMillan, DWC
首次完成了富电子苯环与α，β-不饱和醛的不对称选择性有机催化烷基化反应。苄基是天然产物和药物合成的重要手性合成子，亚胺盐催化的应用为苄基立体异构体的不对称选择性构建提供了一种新的策略。已发现（2S，5S）-5-苄基-2-叔丁基咪唑烷酮胺催化剂介导多种取代和未取代的苯胺与不饱和醛的共轭加成。醛底物的多样性光谱也可以容纳在这种新的有机催化转化。虽然在本研究中通常使用10摩尔%的催化剂量，但描述了用低至1摩尔%的催化剂负载进行的成功烷基化。
The first enantioselective organocatalytic alkylation of electron-rich benzene rings with α,β-unsaturated aldehydes has been accomplished. The use of iminium catalysis has provided a new strategy for the enantioselective construction of benzylic stereogenicity, an important chiral synthon for natural product and medicinal agent synthesis. The (2S,5S)-5-benzyl-2-tert-butylimidazolidinone amine catalyst has been found to mediate the conjugate addition of a wide variety of substituted and unsubstituted anilines to unsaturated aldehydes. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. While catalyst quantities of 10 mol % were generally employed in this study, successful alkylations conducted with catalyst loadings as low as 1 mol % are described.