Reaction scope and mechanistic insights of nickel-catalyzed migratory Suzuki-Miyaura cross-coupling

作者:Li, YQ (Li, Yuqiang)[ 1 ] ; Luo, YX (Luo, Yixin)[ 2 ] ; Peng, L (Peng, Long)[ 1 ] ; Li, YY (Li, Yangyang)[ 1 ] ; Zhao, BZ (Zhao, Binzhi)[ 1 ] ; Wang, W (Wang, Wang)[ 1 ] ; Pang, HL (Pang, Hailiang)[ 1 ] ; Deng, Y (Deng, Yi)[ 1 ] ; Bai, RP (Bai, Ruopeng)[ 2 ] ; Lan, Y (Lan, Yu)[ 2,3 ] ; Yin, GY (Yin, Guoyin)[ 1 ]

NATURE COMMUNICATIONS

卷: 11 期: 1

文献号: 417

DOI: 10.1038/s41467-019-14016-1

出版年: JAN 21 2020

文献类型:Article

摘要

Cross-coupling reactions have developed into powerful approaches for carbon-carbon bond formation. In this work, a Ni-catalyzed migratory Suzuki-Miyaura cross-coupling featuring high benzylic or allylic selectivity has been developed. With this method, unactivated alkyl electrophiles and aryl or vinyl boronic acids can be efficiently transferred to diarylalkane or allylbenzene derivatives under mild conditions. Importantly, unactivated alkyl chlorides can also be successfully used as the coupling partners. To demonstrate the applicability of this method, we showcase that this strategy can serve as a platform for the synthesis of terminal, partially deuterium-labeled molecules from readily accessible starting materials. Experimental studies suggest that migratory cross-coupling products are generated from Ni(0/II) catalytic cycle. Theoretical calculations indicate that the chain-walking occurs at a neutral nickel complex rather than a cationic one. In addition, the original-site cross-coupling products can be obtained by alternating the ligand, wherein the formation of the products has been rationalized by a radical chain process.

关键词

KeyWords Plus:OXIDATIVE-ADDITION; ALKYL BROMIDES; TERTIARY ALKYL; NI; FUNCTIONALIZATION; HALIDES; REMOTE; CARBOXYLATION; ELECTROPHILES; SELECTIVITY

作者信息

通讯作者地址:

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

Chongqing University Chongqing Univ, Sch Chem & Chem Engn, Chongqing Key Lab Theoret & Computat Chem, Chongqing 400030, Peoples R China.

Zhengzhou University Zhengzhou Univ, Coll Chem & Mol Engn, Zhengzhou 450001, 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.

通讯作者地址: Lan, Y (通讯作者)

Chongqing Univ, Sch Chem & Chem Engn, Chongqing Key Lab Theoret & Computat Chem, Chongqing 400030, Peoples R China.

通讯作者地址: Lan, Y (通讯作者)

Zhengzhou Univ, Coll Chem & Mol Engn, Zhengzhou 450001, Peoples R China.

地址:

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

[ 2 ]‎ Chongqing Univ, Sch Chem & Chem Engn, Chongqing Key Lab Theoret & Computat Chem, Chongqing 400030, Peoples R China

[ 3 ]‎ Zhengzhou Univ, Coll Chem & Mol Engn, Zhengzhou 450001, Peoples R China

电子邮件地址:lanyu@cqu.edu.cn; yinguoyin@whu.edu.cn