title: Palladacycle-catalyzed asymmetric hydrophosphination of enones for synthesis of C*- and P*-chiral tertiary phosphines.
abstract: A highly reactive and stereoselective hydrophosphination of enones catalyzed by palladacycles for the synthesis of C*- and P*-chiral tertiary phosphines has been developed. When Ph(2)PH was employed as the hydrophosphinating reagent, a series of C*-chiral tertiary phosphines were synthesized (C*-P bond formation) in high yields with excellent enantioselectivities, and a single recrystallization provides access to their enantiomerically pure forms. When racemic secondary phosphines rac-R(3)(R(4))PH were utilized, a series of tertiary phosphines containing both C*- and P*-chiral centers were generated (C*-P* bond formation) in high yields with good diastereo- and enantioselectivities. The stereoelectronic factors involved in the catalytic cycle have been revealed.
authors.affiliation: Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
authors.forename: Yinhua
authors.initials: Y
authors.lastname: Huang
authors.forename: Sumod A
authors.initials: SA
authors.lastname: Pullarkat
authors.forename: Yongxin
authors.initials: Y
authors.lastname: Li
authors.forename: Pak-Hing
authors.initials: PH
authors.lastname: Leung