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SET-induced biaryl cross-coupling: an S(RN)1 reaction.

ABSTRACT: The SET-induced biaryl cross-coupling reaction is established as the first example of a Grignard S(RN)1 reaction. The reaction is examined within the mechanistic framework of dissociative electron transfer in the presence of a Lewis acid. DFT calculations show that the reaction proceeds through a radical intermediate in the form of an Mg ion-radical cage, which eludes detection in trapping experiments by reacting quickly to form an MgPh2 radical anion intermediate. A new mechanism is proposed.

SUBMITTER: Haines BE

PROVIDER: S-EPMC3985438 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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SET-induced biaryl cross-coupling: an S(RN)1 reaction.

Haines Brandon E BE Wiest Olaf O

The Journal of organic chemistry 20140306 6

The SET-induced biaryl cross-coupling reaction is established as the first example of a Grignard S(RN)1 reaction. The reaction is examined within the mechanistic framework of dissociative electron transfer in the presence of a Lewis acid. DFT calculations show that the reaction proceeds through a radical intermediate in the form of an Mg ion-radical cage, which eludes detection in trapping experiments by reacting quickly to form an MgPh2 radical anion intermediate. A new mechanism is proposed. ...[more]

PMID: 24564385

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