The first enantioselective organocatalytic Mukaiyama- Michael reaction:: A direct method for the synthesis of enantioenriched γ-butenolide architecture
The first enantioselective organocatalytic Mukaiyama- Michael reaction:: A direct method for the synthesis of enantioenriched γ-butenolide architecture
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DOI：
10.1021/ja029095q
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发表时间：
2003-02-05
影响因子：
15
通讯作者：
MacMillan, DWC
中科院分区：
文献类型：
--
作者：
Brown, SP;Goodwin, NC;MacMillan, DWC
第一个使用α，β-不饱和醛的对映选择性有机催化Mukaiyama-Michael反应已经完成。亚胺盐催化剂的使用为2-甲硅氧基呋喃与不饱和醛的对映选择性加成提供了一种新的策略，以产生各种丁烯酰亚胺体系，丁烯酰亚胺是许多天然分离物中发现的重要手性合成子。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甲硅烷基氧基呋喃与不饱和醛的共轭加成。一个不同的范围内的醛类底物可以容纳在这个新的有机催化转化。本文还讨论了这种新的不对称技术在刺孢青霉酸及其5-表刺孢青霉酸类似物的不对称全合成中的应用。
The first enantioselective organocatalytic Mukaiyama−Michael reaction using α,β-unsaturated aldehydes has been accomplished. The use of iminium catalysis has provided a new strategy for the enantioselective addition of 2-silyloxy furans to unsaturated aldehydes to generate a variety of butenolide systems, an important chiral synthon found among many natural isolates. The (2S,5S)-5-benzyl-2-tert-butyl-imidazolidinone amine catalyst has been found to mediate the conjugate addition of a wide variety of substituted and unsubstituted silyloxy furans to unsaturated aldehydes. A diverse range of aldehyde substrates can be accommodated in this new organocatalytic transformation. Application of this new asymmetric technology to the enantioselective total synthesis of spiculisporic acid and the corresponding 5-epi-spiculisporic acid analogue is also discussed.