An Example of the Persistent Radical Effect in Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling

Bruce P. Branchaud; Gui Xue Yu

doi:10.1021/om00035a002

An Example of the Persistent Radical Effect in Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling

Bruce P. Branchaud, Gui Xue Yu

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Photolysis of alkylcobaloximes in the presence of activated alkenes results in both β-H elimination and alkyl–alkenyl cross coupling. A proposed mechanism predicts that buildup of the persistent radical ⋅Co^II- (dmgH)₂py as the reactions proceed enhances β-H elimination, lowering the yield of cross coupling. Scavengers of ⋅Co^II(dmgH)₂py suppress β-H elimination and enhance cross coupling, presumably by lowering the concentration of ⋅Co^II(dmgH)₂py. These data provide support for the proposed reaction mechanism and illustrate how a persistent radical can control product distributions in an organometallic radical reaction.

Original language	English (US)
Pages (from-to)	4262-4264
Number of pages	3
Journal	Organometallics
Volume	12
Issue number	11
DOIs	https://doi.org/10.1021/om00035a002
State	Published - 1993
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "An Example of the Persistent Radical Effect in Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling",

abstract = "Photolysis of alkylcobaloximes in the presence of activated alkenes results in both β-H elimination and alkyl–alkenyl cross coupling. A proposed mechanism predicts that buildup of the persistent radical ⋅CoII- (dmgH)2py as the reactions proceed enhances β-H elimination, lowering the yield of cross coupling. Scavengers of ⋅CoII(dmgH)2py suppress β-H elimination and enhance cross coupling, presumably by lowering the concentration of ⋅CoII(dmgH)2py. These data provide support for the proposed reaction mechanism and illustrate how a persistent radical can control product distributions in an organometallic radical reaction.",

author = "Branchaud, {Bruce P.} and Yu, {Gui Xue}",

year = "1993",

doi = "10.1021/om00035a002",

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AU - Branchaud, Bruce P.

AU - Yu, Gui Xue

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Y1 - 1993

N2 - Photolysis of alkylcobaloximes in the presence of activated alkenes results in both β-H elimination and alkyl–alkenyl cross coupling. A proposed mechanism predicts that buildup of the persistent radical ⋅CoII- (dmgH)2py as the reactions proceed enhances β-H elimination, lowering the yield of cross coupling. Scavengers of ⋅CoII(dmgH)2py suppress β-H elimination and enhance cross coupling, presumably by lowering the concentration of ⋅CoII(dmgH)2py. These data provide support for the proposed reaction mechanism and illustrate how a persistent radical can control product distributions in an organometallic radical reaction.

AB - Photolysis of alkylcobaloximes in the presence of activated alkenes results in both β-H elimination and alkyl–alkenyl cross coupling. A proposed mechanism predicts that buildup of the persistent radical ⋅CoII- (dmgH)2py as the reactions proceed enhances β-H elimination, lowering the yield of cross coupling. Scavengers of ⋅CoII(dmgH)2py suppress β-H elimination and enhance cross coupling, presumably by lowering the concentration of ⋅CoII(dmgH)2py. These data provide support for the proposed reaction mechanism and illustrate how a persistent radical can control product distributions in an organometallic radical reaction.

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JF - Organometallics

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ER -

An Example of the Persistent Radical Effect in Cobaloxime-Mediated Radical Alkyl-Alkenyl Cross Coupling

Abstract

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