Stereoselective synthesis of pentasubstituted 1,3-dienesviaNi-catalyzed reductive coupling of unsymmetrical internal alkynes

作者:Zhou, ZJ (Zhou, Zhijun)[ 1 ] ; Chen, JC (Chen, Jiachang)[ 1 ] ; Chen, HR (Chen, Herong)[ 1 ] ; Kong, WQ (Kong, Wangqing)[ 1 ]

CHEMICAL SCIENCE

卷: 11 期: 37 页: 10204-10211

DOI: 10.1039/d0sc04173d

出版年: OCT 7 2020

文献类型:Article

摘要

The reductive coupling of alkynes represents a powerful strategy for the rapid synthesis of highly substituted 1,3-dienes. This method has the advantages of high atom and step economy, and readily available substrates. Unfortunately, the intermolecular coupling of unsymmetrical internal alkynes remains extremely challenging due to the difficulty in controlling self-dimerization and cross-coupling, as well as stereo- and regioselectivity. Previous reports are still limited to intramolecular processes or the use of stoichiometric amounts of metal catalyst. Herein, we report that nickel-catalyzed reductive coupling of two unsymmetrical internal alkynes can overcome the above-mentioned limitations by using a hemilabile directing group strategy to control the regioselectivity. A series of synthetically challenging penta-substituted 1,3-dienes are obtained in good yields with high regio- and enantioselectivity (mostly > 20/1 rr, >90% ee).

关键词

KeyWords Plus:CATALYZED BORYLATIVE CYCLIZATION; ALLYLIC ALCOHOLS; C-C; ENANTIOSELECTIVE SYNTHESIS; ALKENES; LIGAND; 1,3-DIENES; 1,6-ENYNES; ALDEHYDES; PHOSPHATES

作者信息

通讯作者地址:

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

通讯作者地址: Kong, WQ (通讯作者)

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

地址:

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

电子邮件地址:wqkong@whu.edu.cn