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Asymmetric synthesis of bis(tertiary arsines): Highly stereoselective alkylations of diastereomers of a chiral phosphine-stabilized bis(arsenium triflate)

Citation

Weir, ML and Cade, IA and Kilah, NL and Zhou, X and Wild, SB, Asymmetric synthesis of bis(tertiary arsines): Highly stereoselective alkylations of diastereomers of a chiral phosphine-stabilized bis(arsenium triflate), Inorganic Chemistry, 48, (15) pp. 7482-7490. ISSN 0020-1669 (2009) [Refereed Article]

Copyright Statement

Copyright 2009 American Chemical Society

DOI: doi:10.1021/ic900797y

Abstract

The addition of organolithium reagents to an equilibrating mixture of diastereomers of a phosphine-stabilized 1,2-ethanediylbis(phenylarsenium triflate) containing chiral arsenic stereocenters and an enantiomerically pure, atropisomeric tertiary phosphepine derived from lithiated (aR)-2,2' -dimethyl-1,1'-binaphthalene generates unequal mixtures of diastereomers and enantiomers of chelating 1,2-ethanediylbis(tertiary arsines), chiral at arsenic, with liberation of the (aRP)-phosphepine. Thus, the addition of methyllithium in diethyl ether at -95C to a dichloromethane solution of the complex (R*As,R*As)-()/(R*As,SAs)-1,2[(R3P)PhAsCH2CH2AsPh(PR3)](OTf)2, where R3P is (aRP)-[2-(methoxymethyl)phenyl]phosphepine, generates (R*As,R*As)-(()-1,2-ethanediylbis(methylphenylarsine) in 78% diastereoselectivity and 95% enantioselectivity in favor of the (RAs,RAs) enantiomer. Under similar conditions, the addition of n-butyllithium in hexanes to a solution of the bis(phosphepine-stabilized)-diarsenium triflate at-95C gives the corresponding (R*As,R*As)-()-1,2-ethanediylbis[(n-butyl)phenylarsine) in 77% diastereoselectivity and 93% enantioselectivity in favor of the (RAs,RAs) enantiomer.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Non-metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Kilah, NL (Dr Nathan Kilah)
ID Code:84263
Year Published:2009
Web of Science® Times Cited:10
Deposited By:Chemistry
Deposited On:2013-05-01
Last Modified:2015-01-21
Downloads:0

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