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A palladium-catalyzed alkyl C-H borylation with bromide as a traceless directing group is described, providing a convenient approach to access alkyl boronates bearing a β-all-carbon quaternary stereocenter. The protocol features a broad substrate scope, excellent site selectivity, and good functional group tolerance.A palladium/norbornene cooperative catalyzed selective C-H bond amination of aryl iodides was explored, providing an efficient tool for constructing benzocyclic molecules. When ortho-substituted iodobenzene was involved, the C