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Synthesis and characterization of a pair of O-fac/O-mer 12-P-6 alkyloxaphosphates with a P-O-C-C four-membered ring.

ABSTRACT: Structurally characterized hexacoordinate organophosphorus compounds remain rare due to their highly reactive nature and thermal instability. Herein we report the first synthesis of a pair of O-facial and O-meridional hexacoordinate oxaphosphates (5B and 5D) obtained from the O-apical and O-equatorial ?-hydroxyalkylphosphoranes 3 and 4. This was achieved by using the bulky C₂F₅-groups on the ortho-substituted aryl backbone. Calculations of the relative energies of possible isomers indicate 5B and 5D are thermodynamic products. Although the mechanisms of their formation and the determining factor of stereo-selectivity are still unclear, their isolation and structure conformation contributes to a formulation of a viable strategy for diastereoselective synthesis of heteroleptic hexacoordinate organophosphates.

SUBMITTER: Jiang XD

PROVIDER: S-EPMC6432329 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Synthesis and characterization of a pair of O-fac/O-mer 12-P-6 alkyloxaphosphates with a P-O-C-C four-membered ring.

Jiang Xin-Dong XD Toya Yuya Y Matsukawa Shiro S Kojima Satoshi S Jimenez-Halla J Oscar C JOC Shang Rong R Nakamoto Masaaki M Yamamoto Yohsuke Y

Chemical science 20190219 12

Structurally characterized hexacoordinate organophosphorus compounds remain rare due to their highly reactive nature and thermal instability. Herein we report the first synthesis of a pair of O-facial and O-meridional hexacoordinate oxaphosphates (5B and 5D) obtained from the O-apical and O-equatorial β-hydroxyalkylphosphoranes 3 and 4. This was achieved by using the bulky C2F5-groups on the ortho-substituted aryl backbone. Calculations of the re ...[more]

PMID: 30996936

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