Configurationally homogeneous diastereomers of a linear hexa(tertiary phosphine):: Enantioselective self-assembly of a double-stranded parallel helicate of the type (P)-[Cu3(hexaphos)2](PF6)3

被引：44

作者：

Bowyer, PK ^{[1
]}

Cook, VC ^{[1
]}

Gharib-Naseri, N ^{[1
]}

Gugger, PA ^{[1
]}

Rae, AD ^{[1
]}

Swiegers, GF ^{[1
]}

Willis, AC ^{[1
]}

Zank, J ^{[1
]}

Wild, SB ^{[1
]}

机构：

[1] Australian Natl Univ, Res Sch Chem, Canberra, ACT 0200, Australia

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2002年 / 99卷 / 08期

关键词：

D O I：

10.1073/pnas.072640699

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Three configurationally homogeneous diastereomers of the linear hexa(tertiary phosphine) Ph2PCH2CH2P(Ph)CH2CH2P(Ph)CH2CH2P(Ph)CH2CH2P(Ph)CH2CH2PPh2 (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(l) 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 Pconfiguration that determines the stereochemistry of the parallel and double alpha-helix conformers of the double-stranded trinuclear metal helicate.

引用

页码：4877 / 4882

页数：6

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