Synthesis and Optical Resolution of Aminophosphines with Axially Chiral C(aryl)−N(amine) Bonds for Use as Ligands in Asymmetric Catalysis

Autor:	Youtaro Hattori, Hiroaki Saotome, Masami Sakamoto, Youichi Tanaka, Takashi Mino, Toshihiro Yabusaki, Tsutomu Fujita
Rok vydání:	2006
Předmět:	Atropisomer chemistry.chemical_compound Tsuji–Trost reaction chemistry Nucleophilic aromatic substitution Stereochemistry Aryl Organic Chemistry Nucleophilic substitution Enantioselective synthesis Enantiomeric excess Medicinal chemistry Phosphine
Zdroj:	The Journal of Organic Chemistry. 71:7346-7353
ISSN:	1520-6904 0022-3263
DOI:	10.1021/jo061261f
Popis:	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).
Databáze:	OpenAIRE
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