Asymmetric One‐Pot Mukaiyama Michael/Michael Reaction Catalyzed by Diphenylprolinol Silyl Ether
Asymmetric One‐Pot Mukaiyama Michael/Michael Reaction Catalyzed by Diphenylprolinol Silyl Ether
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DOI：
10.1002/ejoc.202000925
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发表时间：
2020-09
影响因子：
2.8
通讯作者：
Nariyoshi Umekubo;Y. Hayashi
中科院分区：
文献类型：
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作者：
Nariyoshi Umekubo;Y. Hayashi
在二苯基脯氨醇硅醚催化下，α，β-不饱和醛与环酮烯醇醚的不对称催化Mukaiyama Michael反应得到了具有良好的非对映选择性和对映选择性的Michael产物.双环[2.2.2]辛酮衍生物可以通过两步一锅反应以几乎光学纯的形式合成为单一异构体，所述两步一锅反应包括由二烯醇甲硅烷基醚和α，β-不饱和醛开始的由二苯基脯氨醇甲硅烷基醚催化的顺序的Mukaiyama Michael反应和分子内Michael反应。在第二次Michael反应中，正动力学拆分发生，增加了对映选择性。
The asymmetric catalytic Mukaiyama Michael reaction between α,β‐unsaturated aldehydes and silyl enol ether derived from a cyclic ketone was catalyzed by diphenylprolinol silyl ether to afford Michael products with excellent diastereo‐ and enantioselectivities. Bicyclo[2.2.2]octanone derivatives can be synthesized as a single isomer in a nearly optically pure form via a two‐step, one‐pot reaction, comprising the sequential Mukaiyama Michael reaction and intramolecular Michael reaction starting from dienol silyl ether and α,β‐unsaturated aldehydes, catalyzed by diphenylprolinol silyl ether. In the second Michael reaction, positive kinetic resolution occurred to increase the enantioselectivity.