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.