title: Efficient asymmetric synthesis of structurally diverse P-stereogenic phosphinamides for catalyst design.
abstract: The use of chiral phosphinamides is relatively unexplored because of the lack of a general method for the synthesis. Reported herein is the development of a general, efficient, and highly enantioselective method for the synthesis of structurally diverse P-stereogenic phosphinamides. The method relies on nucleophilic substitution of a chiral phosphinate derived from the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide. These chiral phosphinamides were utilized for the first synthesis of readily tunable P-stereogenic Lewis base organocatalysts, which were used successfully for highly enantioselective catalysis.
authors.affiliation: Department of Chemical Development, Boehringer Ingelheim Pharmaceuticals Inc. 900 Ridgebury Road, Ridgefield, CT 06877 (USA). steve.han@boehringer-ingelheim.com.
authors.forename: Zhengxu S
authors.initials: ZS
authors.lastname: Han
authors.forename: Li
authors.initials: L
authors.lastname: Zhang
authors.forename: Yibo
authors.initials: Y
authors.lastname: Xu
authors.forename: Joshua D
authors.initials: JD
authors.lastname: Sieber
authors.forename: Maurice A
authors.initials: MA
authors.lastname: Marsini
authors.forename: Zhibin
authors.initials: Z
authors.lastname: Li
authors.forename: Jonathan T
authors.initials: JT
authors.lastname: Reeves
authors.forename: Keith R
authors.initials: KR
authors.lastname: Fandrick
authors.forename: Nitinchandra D
authors.initials: ND
authors.lastname: Patel
authors.forename: Jean-Nicolas
authors.initials: JN
authors.lastname: Desrosiers
authors.forename: Bo
authors.initials: B
authors.lastname: Qu
authors.forename: Anji
authors.initials: A
authors.lastname: Chen
authors.forename: DiAndra M
authors.initials: DM
authors.lastname: Rudzinski
authors.forename: Lalith P
authors.initials: LP
authors.lastname: Samankumara
authors.forename: Shengli
authors.initials: S
authors.lastname: Ma
authors.forename: Nelu
authors.initials: N
authors.lastname: Grinberg
authors.forename: Frank
authors.initials: F
authors.lastname: Roschangar
authors.forename: Nathan K
authors.initials: NK
authors.lastname: Yee
authors.forename: Guijun
authors.initials: G
authors.lastname: Wang
authors.forename: Jinhua J
authors.initials: JJ
authors.lastname: Song
authors.forename: Chris H
authors.initials: CH
authors.lastname: Senanayake
mesh_terms: D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic; D058115:Lewis Bases / Q000737:chemistry*; D015394:Molecular Structure; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D010721:Phosphinic Acids / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000577:Amides; D058115:Lewis Bases; D010720:Phosphines; D010721:Phosphinic Acids
keywords: asymmetric catalysis; chirality; nucleophilic substitution; organocatalyst; phosphinamides