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. 2012 Oct 3;134(39):16131-4.
doi: 10.1021/ja306446m. Epub 2012 Sep 19.

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

R David Grigg  1 , Ryan Van Hoveln, Jennifer M Schomaker
Affiliations

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

R David Grigg et al. J Am Chem Soc. .

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.

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Figures

Scheme 1
Scheme 1
Traditional cross-coupling approach vs. a new mode of arene functionalization.
Scheme 2
Scheme 2
Recycling of the activating group.
Scheme 3
Scheme 3
Cross-over experiment using isotopically enriched 79Br.
Scheme 4
Scheme 4
A potential mechanism for the Cu-catalyzed 1,3-halogen migration.
See this image and copyright information in PMC

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