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Cobalt-Catalyzed Regioselective Olefin Isomerization Under Kinetic Control.

Authors
  • Liu, Xufang1
  • Zhang, Wei1
  • Wang, Yujie1
  • Zhang, Ze-Xin1
  • Jiao, Lei1
  • Liu, Qiang1
  • 1 Center of Basic Molecular Science (CBMS), Department of Chemistry , Tsinghua University , Beijing 100084 , China. , (China)
Type
Published Article
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Publication Date
Jun 06, 2018
Volume
140
Issue
22
Pages
6873–6882
Identifiers
DOI: 10.1021/jacs.8b01815
PMID: 29781616
Source
Medline
License
Unknown

Abstract

Olefin isomerization is a significant transformation in organic synthesis, which provides a convenient synthetic route for internal olefins and remote functionalization processes. The selectivity of an olefin isomerization process is often thermodynamically controlled. Thus, to achieve selectivity under kinetic control is very challenging. Herein, we report a novel cobalt-catalyzed regioselective olefin isomerization reaction. By taking the advantage of fine-tunable NNP-pincer ligand structures, this catalytic system features high kinetic control of regioselectivity. This mild catalytic system enables the isomerization of 1,1-disubstituted olefins bearing a wide range of functional groups in excellent yields and regioselectivity. The synthetic utility of this transformation was highlighted by the highly selective preparation of a key intermediate for the total synthesis of minfiensine. Moreover, a new strategy was developed to realize the selective monoisomerization of 1-alkenes to 2-alkenes dictated by installing substituents on the γ-position of the double bonds. Mechanistic studies supported that the in situ generated Co-H species underwent migratory insertion of double bond/β-H elimination sequence to afford the isomerization product. The less hindered olefin products were always preferred in this cobalt-catalyzed olefin isomerization due to an effective ligand control of the regioselectivity for the β-H elimination step.

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