Open AccessCatalytic [5 + 1]-Cycloadditions of Vinylcyclopropanes and Vinylidenes
Author(s) -
Conner M. Farley,
Kohei Sasakura,
YouYun Zhou,
Vibha V Kanale,
Christopher Uyeda
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c00356
Subject(s) - cycloaddition , chemistry , cobalt , catalysis , stoichiometry , medicinal chemistry , combinatorial chemistry , organic chemistry
Polysubstituted cyclohexenes bearing 1,3 ( meta ) substitution patterns are challenging to access using the Diels-Alder reaction (the ortho - para rule). Here, we report a cobalt-catalyzed reductive [5 + 1]-cycloaddition between a vinylcyclopropane and a vinylidene to provide methylenecyclohexenes bearing all- meta relationships. Vinylidene equivalents are generated from 1,1-dichloroalkenes using Zn as a stoichiometric reductant. Experimental observations are consistent with a mechanism involving a cobaltacyclobutane formed from a [2 + 2]-cycloaddition between a cobalt vinylidene and a vinylcyclopropane.