Mechanistic
Interrogation of Co/Ni-Dual Catalyzed Hydroarylation
Version 4 2018-09-21, 18:33
Version 3 2018-09-21, 18:20
Version 2 2018-09-18, 14:18
Version 1 2018-09-18, 12:18
Posted on 2018-09-21 - 18:33
Cobalt/nickel-dual
catalyzed hydroarylation of terminal olefins with iodoarenes builds
complexity from readily available starting materials, with a high
preference for the Markovnikov (branched) product. Here, we advance
a mechanistic model of this reaction through the use of reaction progress
kinetic analysis (RPKA), radical clock experiments, and stoichiometric
studies. Through exclusion of competing hypotheses, we conclude that
the reaction proceeds through an unprecedented alkylcobalt to nickel
direct transmetalation. Demonstration of catalytic alkene prefunctionalization,
via spectroscopic observation of an organocobalt species, distinguishes
this Csp2–Csp3 cross-coupling method
from a conventional transmetalation process, which employs a stoichiometric
organometallic nucleophile, and from a bimetallic oxidative addition
of an organohalide across nickel, described by radical scission and
subsequent alkyl radical capture at a second nickel center. A refined
understanding of the reaction leads to an optimized hydroarylation
procedure that excludes exogenous oxidant, demonstrating that the
transmetalation is net redox neutral. Catalytic alkene prefunctionalization
by cobalt and engagement with nickel catalytic cycles through direct
transmetalation provides a new platform to merge these two rich areas
of chemistry in preparatively useful ways.
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Shevick, Sophia L.; Obradors, Carla; Shenvi, Ryan A. (2018). Mechanistic
Interrogation of Co/Ni-Dual Catalyzed Hydroarylation. ACS Publications. Collection. https://doi.org/10.1021/jacs.8b06458
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AUTHORS (3)
SS
Sophia L. Shevick
CO
Carla Obradors
RS
Ryan A. Shenvi
KEYWORDS
reaction proceedsnickel centerorganocobalt speciesCspexogenous oxidantbimetallic oxidative additionspectroscopic observationoptimized hydroarylation proceduretransmetalation processCatalytic alkene prefunctionalizationclock experimentsRPKAreaction progressterminal olefinsalkene prefunctionalizationMechanistic Interrogationstoichiometric organometallic nucleophilestoichiometric studies