title: Copper-Catalyzed Transformations Using Cu-H, Cu-B, and Cu-Si as Active Catalyst Species.
abstract: This review summarizes transformations using copper hydride (Cu-H), boryl copper (Cu-B) or silyl copper (Cu-Si) as active catalyst species. Semihydrogenation, hydroboration, and hydrocarboxylation have been developed using Cu-H as active catalyst species. Preferential reduction of sterically hindered ketones is accompanied by Cu-H species bearing a bowl-shaped phosphine as a crucial ligand. Employing Cu-B species, hydroboration of alkynes and allenes, synthesis of 2-boryl-1,3-butadiene, and borylative allyl-allyl coupling are established. Silacarboxylation of alkynes, regiodivergent silacarboxylation of allenes, and silylative allylation of ketones involve Cu-Si species. The key to these selective transformations is regioselective addition of Cu-H, Cu-B, or Cu-Si species to carbon-carbon multiple bonds of alkynes and allenes to afford the corresponding alkenylcopper or allylcopper intermediates.
authors.affiliation: Department of Energy and Hydrocarbon chemistry Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan. ytsuji@scl.
authors.forename: Yasushi
authors.initials: Y
authors.lastname: Tsuji
authors.affiliation: Department of Energy and Hydrocarbon chemistry Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan.
authors.forename: Tetsuaki
authors.initials: T
authors.lastname: Fujihara
keywords: boron; copper; regioselectivity; silicon; synthesis design