Stereoselective [1,2]-Phospha-Brook Rearrangement of CAMDOL-Derived H-Phosphonate: Synthesis of α-Trifluoromethyl Alcohols

A highly efficient and stereoselective [1,2]-phospha-Brook rearrangement of fluoromethyl ketones has been achieved by utilizing a new type of P-chiral H-phosphonate derived from CAMDOL, designated as CAMDOL-PHO. A library of 38 secondary alcohols featuring an α-trifluoromethyl or trifluoroaryl motif were afforded in up to 97% yield with 99:1 dr. Compared to other known chiral auxiliaries, bicyclic CAMDOL exhibits superior induction ability due to its unique center-chiral scaffold.