Regiocontrolled Reductive Vinylation of Aliphatic 1,3-Dienes with Vinyl Triflates by Nickel Catalysis

The regiocontrolled functionalization of 1,3-dienes has become a powerful tool for divergent synthesis, yet it remains a long-standing challenge for aliphatic substrates. Herein, we report a reductive approach for a branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R–X electrophiles,...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2021-03, Vol.143 (12), p.4536-4542
Main Authors: Pang, Xiaobo, Zhao, Zhen-Zhen, Wei, Xiao-Xue, Qi, Liangliang, Xu, Guang-Li, Duan, Jicheng, Liu, Xue-Yuan, Shu, Xing-Zhong
Format: Article
Language:English
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Summary:The regiocontrolled functionalization of 1,3-dienes has become a powerful tool for divergent synthesis, yet it remains a long-standing challenge for aliphatic substrates. Herein, we report a reductive approach for a branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R–X electrophiles, which represents a new selectivity pattern for diene functionalization. Simple butadiene, aromatic 1,3-dienes, and highly conjugated polyene were also tolerated. The combination of Ni(0) and the phosphine–nitrile ligand generally resulted in >20:1 regioselectivity with the retention of the geometry of the C3–C4 double bonds. This reaction proceeds with a broad substrate scope, and it allows for the conjugation of two biologically active units to form more complex polyene molecules, such as tetraene and pentaene as well as heptaene.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c00142