P‑Stereogenic Bicyclo[4.3.1]phosphite Boranes: Synthesis and Utility of Tunable P‑Tether Systems for the Desymmetrization of C2‑Symmetric 1,3-anti-Diols

The development of P-stereogenic bicyclo[4.3.1]­phosphite borane tether systems for the desymmetrization of C2-symmetric dienediols is reported. This report highlights preliminary studies including tether installation and removal as well as chemoselective functionalization of the exocyclic olefin via diimide reduction or cross-metathesis. Most notably, a divergent oxidation strategy allows for the transformation of the bicyclic phosphite borane complexes to the corresponding phosphate or thiophosphate systems, highlighting the electronic attenuation of this P-tether system.本研究报道了用于C₂对称二烯二醇去对称化反应的磷手性双环[4.3.1]亚磷酸酯硼烷连接臂（tether）体系的开发。本工作重点介绍了初步研究内容，包括连接臂的引入与脱除，以及通过二亚胺还原或交叉复分解反应对环外烯烃进行化学选择性官能化修饰。尤为值得关注的是，采用发散型氧化策略可将双环亚磷酸酯硼烷络合物转化为相应的磷酸酯或硫代磷酸酯体系，从而凸显了该磷基连接臂体系的电子衰减特性。