TY - JOUR
T1 - Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization
T2 - Facile Access to Acyclic Trisubstituted Alkenes
AU - Zhang, Sheng
AU - Bedi, Deepika
AU - Cheng, Lu
AU - Unruh, Daniel K.
AU - Li, Guigen
AU - Findlater, Michael
N1 - Publisher Copyright:
© 2020 American Chemical Society.
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2020/5/13
Y1 - 2020/5/13
N2 - Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkenes can serve as an alternative approach to trisubstituted alkenes, but it remains underdeveloped owing to issues relating to reaction efficiency and stereoselectivity. Here we show that a novel cobalt catalyst can overcome these challenges to provide an efficient and stereoselective access to a broad range of trisubstituted alkenes. This protocol is compatible with both mono- and dienes and exhibits a good functional group tolerance and scalability. Moreover, it has proven to be a useful tool to construct organic luminophores and a deuterated trisubstituted alkene. A preliminary study of the mechanism suggests that a cobalt-hydride pathway is involved in the reaction. The high stereoselectivity of the reaction is attributed to both a π-πstacking effect and the steric hindrance between substrate and catalyst.
AB - Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkenes can serve as an alternative approach to trisubstituted alkenes, but it remains underdeveloped owing to issues relating to reaction efficiency and stereoselectivity. Here we show that a novel cobalt catalyst can overcome these challenges to provide an efficient and stereoselective access to a broad range of trisubstituted alkenes. This protocol is compatible with both mono- and dienes and exhibits a good functional group tolerance and scalability. Moreover, it has proven to be a useful tool to construct organic luminophores and a deuterated trisubstituted alkene. A preliminary study of the mechanism suggests that a cobalt-hydride pathway is involved in the reaction. The high stereoselectivity of the reaction is attributed to both a π-πstacking effect and the steric hindrance between substrate and catalyst.
UR - http://www.scopus.com/inward/record.url?scp=85086881922&partnerID=8YFLogxK
U2 - 10.1021/jacs.0c02101
DO - 10.1021/jacs.0c02101
M3 - Article
C2 - 32315519
AN - SCOPUS:85086881922
VL - 142
SP - 8910
EP - 8917
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 19
ER -