Investigation of the Reductive Cleavage of BINAP and Application to the Rapid Synthesis of Phospholes

A rapid and easy entry into λ3-phospholes and λ4-phosphole oxides derived from BINAP is reported herein featuring a variety of C and Si substituents and functional groups, as well the investigative work on the mechanistic pathway. DFT calculations using B3LYP functionals have been carried out to rationalize the mechanism. The observed experimental 31P resonance shifts were compared with the calculated shifts of the proposed intermediates after calibration of the shielding tensors. The calculations included the use of polarizable continuum models to take into account solvent effects and were found to be in excellent agreement, providing further evidence for the proposed mechanism.本文报道了一种快速简便的制备策略，可获得源自联萘二苯膦（BINAP）的λ3-磷杂环戊二烯与λ4-磷杂环戊二烯氧化物，该类化合物带有多种碳基、硅基取代基及官能团，同时还对其反应机理路径开展了系统研究。本研究采用B3LYP泛函进行密度泛函理论（Density Functional Theory，DFT）计算以阐明该反应机理。在对屏蔽张量进行校准后，将实验观测得到的31P核磁共振化学位移与所提出的中间体的理论计算化学位移进行了对比。计算过程中引入可极化连续介质模型以考量溶剂效应，结果显示计算值与实验数据高度吻合，为所提出的反应机理提供了进一步的佐证。