title: Novel Water-Soluble Bisphosphinite Chiral Ligands Derived from alpha,alpha- and beta,beta-Trehalose. Application to Asymmetric Hydrogenation of Dehydroamino Acids and Their Esters in Water or an Aqueous/Organic Biphasic Medium.
abstract: Novel 2,3:4,6-di-O-isopropylidene-alpha-D-glucopyranosyl-(1,1)-4,6-O-isopropylidene-2,3-di-O-diphenylphosphino-alpha-D-glucopyranoside (2), 2,3:4,6-di-O-cyclohexylidene-alpha-D-glucopyranosyl-(1,1)-4,6-O-cyclohexylidene-2,3-di-O-diphenylphosphino-alpha-D-glucopyranoside (4), and 2,3:4,6-di-O-cyclohexylidene-beta-D-glucopyranosyl-(1,1)-4,6-O-cyclohexylidene-2,3-di-O-diphenylphosphino-beta-D-glucopyranoside (11) were prepared from the corresponding alpha,alpha- or beta,beta-trehalose. The ligands were transformed into cationic Rh complexes, such as [Rh(alpha-D-glucopyranosyl-(1,1)-2,3-di-O-diphenylphosphino-alpha-D-glucopyranoside)(cod)]BF(4) (3) and [Rh(beta-D-glucopyranosyl-(1,1)-2,3-di-O-diphenylphosphino-beta-D-glucopyranoside)(cod)]BF(4) (12) bearing free hydroxy groups. These complexes were soluble in water and were efficient catalysts for the asymmetric hydrogenation of dehydroamino acids and their esters in water or an aqueous/organic biphasic medium with high enantioselectivity (up to 99.9% ee). Aqueous biphasic systems offer an easy separation of the aqueous catalyst phase from the product phase and allow recycling of the catalyst phase without the loss of enantioselectivity.
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
authors.forename: Koji
authors.initials: K
authors.lastname: Yonehara
authors.forename: Tomohiro
authors.initials: T
authors.lastname: Hashizume
authors.forename: Kenji
authors.initials: K
authors.lastname: Mori
authors.forename: Kouichi
authors.initials: K
authors.lastname: Ohe
authors.forename: Sakae
authors.initials: S
authors.lastname: Uemura