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Chiral tether-mediated stabilization and helix-sense control of complementary metallo-double helices.


ABSTRACT: A series of novel PtII-linked double helices were prepared by inter- or intrastrand ligand-exchange reactions of the complementary duplexes composed of chiral or achiral amidine dimer and achiral carboxylic acid dimer strands joined by trans-PtII-acetylide complexes with PPh3 ligands using chiral and achiral chelating diphosphines. The structure and stability of the PtII-linked double helices were highly dependent on the diphosphine structures. An interstrand ligand exchange took place with chiral and achiral 1,3-diphosphine-based ligands, resulting in trans-PtII-bridged double helices, whose helical structures were quite stable even in dimethyl sulfoxide (DMSO) due to the interstrand cross-link, whereas a 1,2-diphosphine-based ligand produced non-cross-linked cis-PtII-linked duplexes, resulting from an intrastrand ligand-exchange that readily dissociated into single strands in DMSO. When enantiopure 1,3-diphosphine-based ligands were used, the resulting trans-PtII-bridged double helices adopted a preferred-handed helical sense biased by the chirality of the bridged diphosphines. Interestingly, the interstrand ligand exchange with racemic 1,3-diphosphine toward an optically-active PtII-linked duplex, composed of chiral amidine and achiral carboxylic acid strands, was found to proceed in a diastereoselective manner, thus forming complete homochiral trans-PtII-bridged double helices via a unique chiral self-sorting.

SUBMITTER: Horie M 

PROVIDER: S-EPMC5494540 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature

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Chiral tether-mediated stabilization and helix-sense control of complementary metallo-double helices.

Horie Miki M   Ousaka Naoki N   Taura Daisuke D   Yashima Eiji E  

Chemical science 20140910 1


A series of novel Pt<sup>II</sup>-linked double helices were prepared by inter- or intrastrand ligand-exchange reactions of the complementary duplexes composed of chiral or achiral amidine dimer and achiral carboxylic acid dimer strands joined by <i>trans</i>-Pt<sup>II</sup>-acetylide complexes with PPh<sub>3</sub> ligands using chiral and achiral chelating diphosphines. The structure and stability of the Pt<sup>II</sup>-linked double helices were highly dependent on the diphosphine structures.  ...[more]

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