Preparation of enantiomerically pure 2'-substituted 2-diphenylphosphino-1,1'-binaphthyls by reductive cleavage of the carbon-phosphorus bond in a borane complex of 2-diphenylphosphino-2'-diphenylphosphinyl-1,1'-binaphthyl

T Shimada; H Kurushima; Y H Cho; T Hayashi

doi:10.1021/jo010691x

Preparation of enantiomerically pure 2'-substituted 2-diphenylphosphino-1,1'-binaphthyls by reductive cleavage of the carbon-phosphorus bond in a borane complex of 2-diphenylphosphino-2'-diphenylphosphinyl-1,1'-binaphthyl

J Org Chem. 2001 Dec 28;66(26):8854-8. doi: 10.1021/jo010691x.

Authors

T Shimada¹, H Kurushima, Y H Cho, T Hayashi

Affiliation

¹ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan.

PMID: 11749615
DOI: 10.1021/jo010691x

Abstract

Reaction of (S)-2'-boranatodiphenylphosphino-2-diphenylphosphinyl-1,1'-binaphthyl (3, borane complex of BINAP monoxide) with an excess of n-butyllithium in THF at -78 degrees C brought about a selective cleavage of the carbon-phosphorus bond between the binaphthyl and diphenylphosphinyl groups to generate the binaphthyllithium 14, the treatment of which with electrophiles MeOD, I(2), and ClSnMe(3) gave, after removal of the borane, the corresponding 2'-substituted 2-diphenylphosphino-1,1'-binaphthyls (E-MOP 9: E = D, I, SnMe(3)), without loss of the enantiomeric purity.