1400743-00-1Relevant articles and documents
Development of N-Heterocyclic Carbene-Copper Complexes for 1,3-Halogen Migration
Schmid, Steven C.,Van Hoveln, Ryan,Rigoli, Jared W.,Schomaker, Jennifer M.
, p. 4164 - 4173 (2015/09/01)
A series of NHC-copper complexes was synthesized and their potential to catalyze 1,3-halogen migration explored. Increasing the steric bulk around the metal drastically improves the lifetime of NHC-CuH species and promotes 1,3-halogen migration of both 2-
Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration
Grigg, R. David,Van Hoveln, Ryan,Schomaker, Jennifer M.
supporting information, p. 16131 - 16134,4 (2020/09/09)
A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp2 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 sp3 C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.