Copper-Catalyzed Enantioselective Allylic Alkylation of Terminal Alkyne Pronucleophiles

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• 作者：Ayumi Harada ; Yusuke Makida ; Tatsunori Sato ; Hirohisa Ohmiya ; Masaya Sawamura
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：October 1, 2014
• 年：2014
• 卷：136
• 期：39
• 页码：13932-13939
• 全文大小：536K
• ISSN：1520-5126

文摘

The copper-catalyzed enantioselective allylic alkylation of terminal alkynes with primary allylic phosphates was developed by the use of a new chiral N-heterocyclic carbene ligand bearing a phenolic hydroxy group at the ortho position of one of the two N-aryl groups. This reaction occurred with excellent 纬-branch regioselectivity and high enantioselectivity, forming a controlled stereogenic center at the allylic/propargylic position. Various terminal alkynes, including silyl, aliphatic, and aromatic alkynes, could be used directly without premetalation of the C(sp)鈥揌 bond. On the basis of the results of experiments using an isomeric secondary allylic phosphate, which gave a branched product through an 伪-selective substitution reaction with retention of configuration, a reaction pathway involving 1,3-allylic migration of Cu in a ([蟽 + 蟺]-allyl)copper(III) species is proposed.