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Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

ABSTRACT: A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

SUBMITTER: Grigg RD

PROVIDER: S-EPMC4490833 | biostudies-literature | 2012 Oct

REPOSITORIES: biostudies-literature

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Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

Grigg R David RD Van Hoveln Ryan R Schomaker Jennifer M JM

Journal of the American Chemical Society 20120919 39

A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markov ...[more]

PMID: 22985198

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