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用于构建不对称季碳的C(2)对称手性NHC配体：铜催化格氏试剂对3-取代环己烯酮的共轭加成反应

C(2) symmetric chiral NHC ligand for asymmetric quaternary carbon constructing copper-catalyzed conjugate addition of grignard reagents to 3-substituted cyclohexenones.

作者信息

Matsumoto Yasumasa, Yamada Ken-ichi, Tomioka Kiyoshi

机构信息

Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo, Kyoto, Japan.

出版信息

J Org Chem. 2008 Jun 20;73(12):4578-81. doi: 10.1021/jo800613h. Epub 2008 May 20.

DOI:10.1021/jo800613h
PMID:18489154
Abstract

The asymmetric construction of quaternary carbon centers by conjugate addition of Grignard reagents to 3-methyl- and 3-ethylcyclohexenones was realized in a maximum enantioselectivity of 80% by using a C 2 symmetric chiral N-heterocyclic carbene (NHC)-copper catalyst, generated from (4 S,5 S)-1,3-bis(2-methoxyphenyl)-4,5-diphenyl-4,5-dihydro-1 H-imidazol-3-ium tetrafluoroborate and copper(II) triflate. The stereostructures of the NHC-Au complexes were analyzed by X-ray crystallography, which rationalized the good stereocontrolling ability of N-aryl NHCs.

摘要

通过使用由（4S，5S）-1,3-双（2-甲氧基苯基）-4,5-二苯基-4,5-二氢-1H-咪唑-3-鎓四氟硼酸盐和三氟甲磺酸铜（II）生成的C2对称手性N-杂环卡宾（NHC）-铜催化剂，实现了格氏试剂与3-甲基和3-乙基环己烯酮的共轭加成反应，以最高80%的对映选择性构建了季碳中心。通过X射线晶体学分析了NHC-Au配合物的立体结构，这解释了N-芳基NHCs良好的立体控制能力。

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