Selective Synthesis of C1-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation

Abstract

Directed ortho-lithiation (DoL) has been developed as an effective method for the ortho-substitution of BINOL-phosphoric acid and BINOL-N-triflylphosphoramide (BINOL-P-acids). It can be employed in the rapid assembly of either mono- or disubstituted BINOL-P-acids, including unsymmetrical disubstitution through iterative DoL. Most significantly, DoL has proven to be highly effective in the diastereoselective desymmetrization of pseudo-C2-symmetric BINOL-N-triflylphosphoramide, affording a chiral P-group.