Boron-Copper 1,3-Rearrangement: the New Concept Behind the Boryl Migration from C(sp2) in Alkenyl Boranes to C(sp3)

Regioselective borylcupration of borylated skipped (Z)-dienes generates diborylated alkylcopper species that are involved in an intramolecular stereospecific B/Cu 1,3-rearrangement by migration of Bpin moiety from C(sp(2)) to C(sp(3)). DFT mechanistic studies showed that boryl migration occurs through the formation of 4-membered boracycle intermediate with a moderate free-energy barrier. Moreover, the use of KOMe forms stable Lewis base adducts with Bpin moieties that blocks the reaction. Subsequently to the 1,3-boron shift, the in situ electrophilic trapping allows selective C-H, C-C and C-X bonds, followed by intramolecular cross coupling giving access to cyclic functionalized alkylidenecyclohexanes or alkylidenecyclobutanes.

Automated summary

Regioselective borylcupration of borylated skipped (Z)-dienes generates diborylated alkylcopper species that undergo intramolecular stereospecific B/Cu1,3-rearrangement by migration of Bpin moiety from C(sp(2)) to C(sp(3)). DFT mechanistic studies reveal that boryl migration occurs through the formation of a 4-membered boracycle intermediate with a moderate free-energy barrier. Additionally, the use of KOMe forms stable Lewis base adducts with Bpin moieties, blocking the reaction. Following the 1,3-boron shift, in situ electrophilic trapping enables selective C-H, C-C, and C-X bond formations, leading to cyclic functionalized alkylidenecyclohexanes or alkylidenecyclobutanes.