Jiang Xin-Dong, Toya Yuya, Matsukawa Shiro, Kojima Satoshi, Jimenez-Halla J Oscar C, Shang Rong, Nakamoto Masaaki, Yamamoto Yohsuke
College of Applied Chemistry , Shenyang University of Chemical Technology , Shenyang , 110142 , China.
Department of Chemistry , Graduate School of Science , Hiroshima University , Higashi-hiroshima , 7398526 , Japan . Email:
Chem Sci. 2019 Feb 19;10(12):3466-3472. doi: 10.1039/c8sc05158e. eCollection 2019 Mar 28.
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 ( and ) obtained from the O-apical and O-equatorial β-hydroxyalkylphosphoranes and . This was achieved by using the bulky CF-groups on the ortho-substituted aryl backbone. Calculations of the relative energies of possible isomers indicate and 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.
由于其高反应活性和热不稳定性，结构特征明确的六配位有机磷化合物仍然很少见。在此，我们报告了首例由O-顶端和O-赤道面的β-羟烷基磷烷 和 合成得到的一对O-面式和O-经式六配位氧代磷酸酯（ 和 ）。这是通过在邻位取代的芳基主链上使用庞大的CF基团实现的。对可能异构体相对能量的计算表明 和 是热力学产物。尽管它们的形成机制和立体选择性的决定因素仍不清楚，但它们的分离和结构确证有助于制定一种可行的策略，用于非对映选择性合成杂配六配位有机磷酸酯。
