Nickel-Catalyzed Chemodivergent 1,1-Difunctionalization of Unactivated alpha-Olefins with Alkynyl Electrophiles and B(2)pin(2)

作者:Li, YY (Li, Yangyang)[ 1 ] ; Wei, H (Wei, Hong)[ 1 ] ; Wu, D (Wu, Dong)[ 1 ] ; Li, ZQ (Li, Zheqi)[ 1 ] ; Wang, W (Wang, Wang)[ 1 ] ; Yin, GY (Yin, Guoyin)[ 1 ]

ACS CATALYSIS

卷: 10 期: 9 页: 4888-4894

DOI: 10.1021/acscatal.0c00898

出版年: MAY 1 2020

文献类型:Article

摘要

Divergent catalysis represents a powerful strategy for increasing molecular complexity and exploring catalytic modes in organic synthesis. Herein, we report, a nickel-catalyzed, chemodivergent 1,1-alkynylboration, and 1,1-dialkynylation of unactivated alpha-olefins. This study not only provides an efficient and modular protocol for the divergent synthesis of propargylic boronic esters and gem-dialkynylalkanes, but also achieves a controllable, single or double cross-coupling of Ni/B bimetallic intermediates. Mechanistic studies reveal that the diboron reagent (B-2 pin(2)) plays a significant role in the dialkynylation reaction, serving as both the reductant and transient assisting group. Notably, both reactions show high regioselectivities and good functional group tolerance. In addition, the synthetic value of the products has been demonstrated with several downstream transformations.

关键词

作者关键词:divergent catalysis; nickel catalysis; 1,1-regioselectivity; difunctionalization; alpha-olefins

KeyWords Plus:REGIODIVERGENT; ALKENES; DIFUNCTIONALIZATION; FUNCTIONALIZATION; CONSTRUCTION; ESTERS

作者信息

通讯作者地址:

Wuhan University Wuhan Univ, Inst Adv Studies, Wuhan 430072, Hubei, Peoples R China.

通讯作者地址: Yin, GY (通讯作者)

Wuhan Univ, Inst Adv Studies, Wuhan 430072, Hubei, Peoples R China.

地址:

[ 1 ]‎ Wuhan Univ, Inst Adv Studies, Wuhan 430072, Hubei, Peoples R China

电子邮件地址:yinguoyin@whu.edu.cn