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
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
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DOI：
10.1073/pnas.072640699
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发表时间：
2002-04-16
影响因子：
11.1
通讯作者：
Wild, SB
中科院分区：
文献类型：
--
作者：
Bowyer, PK;Cook, VC;Wild, SB
线性六（叔膦）Ph_2PCH_2CH_2P（Ph）CH_2CH_2P（Ph）CH_2CH_2P（Ph）CH_2CH_2P（Ph）CH_2CH_2P（Ph）CH_2CH_2PPh_2（hexaphos）的三种构型均一的非对映异构体以对映体纯的形式分离出来，即（R，S，S，R）-、（R，S，S，S）-和（S，S，S，S）hexaphos。配体的强螺旋（R，S，S，R）-（-）形式与铜（I）离子结合，通过立体选择性自组装产生[Cu 3（六磷）（2）]（PF 6）（3）型平行螺旋物的P对映体，其已通过X射线晶体学表征。阳离子的理论模型表明，它是两个10元环的螺旋度包含三个铜离子，其中每一个都有扭曲的船椅船构象，和配置的三个手性，四面体铜立体中心的P配置，决定了平行和双α-螺旋构象的双链三核金属螺旋的立体化学之间的关系。
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.