title: Synthesis and optical resolution of aminophosphines with axially chiral C(aryl)-N(amine) bonds for use as ligands in asymmetric catalysis.
abstract: N-Aryl indoline-type aminophosphines 1a-c were obtained in good yields by a nucleophilic aromatic substitution (S(N)Ar) reaction followed by silane reduction. Aminophosphine 1d was also prepared from 2,3-difluorobenzaldehyde (4) via dimethylhydrazone. Optical resolution of C(aryl)-N(amine) bond atropisomers was achieved using (S)-(+)-di-mu-chlorobis[2-[(dimethylamino)ethyl]phenyl-C(2),N]dipalladium(II) ((S)-10). The determination of absolute configuration and the investigation of the rotation barrier for C(aryl)-N(amine) bond axial stability of an aminophosphine 1 are described. Finally, the ability of the chiral phosphine ligand 1 is demonstrated in a catalytic asymmetric reaction, such as a palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate (up to 95% ee).
authors.affiliation: Department of Applied Chemistry and Biotechnology, Faculty of Engineering, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan. tmino@faculty.chiba-u.jp
authors.forename: Takashi
authors.initials: T
authors.lastname: Mino
authors.forename: Youichi
authors.initials: Y
authors.lastname: Tanaka
authors.forename: Youtaro
authors.initials: Y
authors.lastname: Hattori
authors.forename: Toshihiro
authors.initials: T
authors.lastname: Yabusaki
authors.forename: Hiroaki
authors.initials: H
authors.lastname: Saotome
authors.forename: Masami
authors.initials: M
authors.lastname: Sakamoto
authors.forename: Tsutomu
authors.initials: T
authors.lastname: Fujita