title: Acceleration Effects of Phosphine Ligands on the Rhodium-Catalyzed Dehydrogenative Silylation and Germylation of Unactivated C(sp(3))-H Bonds.
abstract: The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp(3))-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C2-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp(3))-H bond. The unprecedented catalytic germylation of C(sp(3))-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.
authors.forename: Masahito
authors.initials: M
authors.lastname: Murai
authors.forename: Hirotaka
authors.initials: H
authors.lastname: Takeshima
authors.forename: Haruka
authors.initials: H
authors.lastname: Morita
authors.affiliation: ‡Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Yoichiro
authors.initials: Y
authors.lastname: Kuninobu
authors.forename: Kazuhiko
authors.initials: K
authors.lastname: Takai