Palladium-Catalyzed Asymmetric Phosphination: Enantioselective Synthesis of a P-Chirogenic Phosphine
- 18 October 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (45) , 13356-13357
- https://doi.org/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.Keywords
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