Palladium-catalyzed asymmetric phosphination: enantioselective synthesis of a p-chirogenic phosphine

Jillian R Moncarz; Natalia F Laritcheva; David S Glueck

doi:10.1021/ja0267324

Palladium-catalyzed asymmetric phosphination: enantioselective synthesis of a p-chirogenic phosphine

J Am Chem Soc. 2002 Nov 13;124(45):13356-7. doi: 10.1021/ja0267324.

Authors

Jillian R Moncarz¹, Natalia F Laritcheva, David S Glueck

Affiliation

¹ 6128 Burke Laboratory, Department of Chemistry, Dartmouth College, Hanover, New Hampshire, 03755, USA.

PMID: 12418867
DOI: 10.1021/ja0267324

Abstract

The racemic secondary phosphine PH(Me)(Is) (1, Is = 2,4,6-(i-Pr)3C6H2) was coupled with PhI in the presence of NaOSiMe3 and the catalyst Pd((R,R)-Me-Duphos)(Ph)(I) (3) to give P(Ph)(Me)(Is) (2) in up to 78% ee. The intermediate phosphido complex Pd((R,R)-Me-Duphos)(Ph)(P(Me)(Is)) (5a,b) was observed as a mixture of diastereomers by low-temperature 31P NMR. The rate of interconversion of 5a,b by phosphorus inversion is greater than or equal to that of reductive elimination, which suggests that the enantiodetermining step occurs after Pd-P bond formation.