Configurationally homogeneous diastereomers of a linear hexa(tertiary phosphine): Enantioselective self-assembly of a double-stranded parallel helicate of the type ( P )-[Cu 3 (hexaphos) 2 ](PF 6 ) 3
Date
2002
Authors
Bowyer, Paul K
Cook, Vernon
Gharib-Naseri, Nahid
Gugger, Paul
Rae, A David
Swiegers, Gerhard
Willis, Anthony
Zank, Johann
Wild, Stanley (Bruce)
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National Academy of Sciences (USA)
Abstract
Three configurationally homogeneous diastereomers of the linear hexa(tertiary phosphine) Ph2PCH2CH2P(Ph) CH2CH2P(Ph)CH2 CH2P-(Ph)CH2CH2P(Ph)CH2 CH2PPh2 (hexaphos) have been isolated in enantiomerically pure form, namely (R,S,S,R)-, (R,S,S,S)-, and (S,S,S,S)-hexaphos. The strongly helicating (R,S,S,R)-(-) form of the ligand combines with copper(I) ions to generate by stereoselective self-assembly the P enantiomer of a parallel helicate of the type [Cu3(hexaphos)2](PF6)3, which has been characterized by x-ray crystallography. Theoretical modeling of the cation indicates that it is the relationship between the helicities of the two 10-membered rings containing the three copper ions, each of which has the twist-boat-chair-boat conformation, and the configurations of the three chiral, tetrahedral copper stereocenters of P configuration that determines the stereochemistry of the parallel and double α-helix conformers of the double-stranded trinuclear metal helicate.
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Keywords
Keywords: cation; copper complex; phosphine derivative; phosphorus derivative; alpha helix; conference paper; conformation; diastereoisomer; enantioselectivity; priority journal; stereochemistry; theoretical model; X ray crystallography; Cations; Chromatography, Hi
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PNAS - Proceedings of the National Academy of Sciences of the United States of America
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Journal article
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2037-12-31