Palladacycle-catalyzed asymmetric hydrophosphination of enones for synthesis of C*- and P*-chiral tertiary phosphines

• Main Authors: Pullarkat, Sumod A., Huang, Yinhua, Li, Yongxin, Leung, Pak-Hing
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2013
• Online Access: https://hdl.handle.net/10356/96850; http://hdl.handle.net/10220/11598
• Institution: Nanyang Technological University

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 Ph2PH 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-R3(R4)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.