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

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

Journal of the American Chemical Society (2012-09-19)
R David Grigg, Ryan Van Hoveln, Jennifer M Schomaker
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.

MATERIALS
Product Number
Brand
Product Description

Supelco
Styrene, analytical standard
Supelco
Styrene, analytical standard
Sigma-Aldrich
Styrene, ReagentPlus®, contains 4-tert-butylcatechol as stabilizer, ≥99%