TY - JOUR
T1 - Configurationally homogeneous diastereomers of a linear hexa(tertiary phosphine)
T2 - Enantioselective self-assembly of a double-stranded parallel helicate of the type (P)-[Cu3(hexaphos)2](PF6)3
AU - Bowyer, Paul K.
AU - Cook, Vernon C.
AU - Gharib-Naseri, Nahid
AU - Gugger, Paul A.
AU - Rae, A. David
AU - Swiegers, Gerhard F.
AU - Willis, Anthony C.
AU - Zank, Johann
AU - Wild, S. Bruce
PY - 2002/4/16
Y1 - 2002/4/16
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0037117635&partnerID=8YFLogxK
U2 - 10.1073/pnas.072640699
DO - 10.1073/pnas.072640699
M3 - Article
SN - 0027-8424
VL - 99
SP - 4877
EP - 4882
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 8
ER -