Deprotonation of secondary benzylic phosphates - configuratiionally stabite benzylic carbanions with a diethoxyphosphoryloxy substituent and their rearrangement to optically active tertiary α-hydroxyphosphonates

Article abstract of DOI:10.1002/cber.19961291217

Optically active alcohols (ee ≥ 98%) such as 1-phenylpropanol, l-(2-naphthyl)ethanol, 1-tetralol, and 1-indanol were transformed into diethyl phosphates 7a-d. sBuLi/TMEDA -induced phosphate-phosphonate rearrangement in diethyl ether furnished tertiatry α-hydroxyphosphonates 8a-d of high enantiomeric purity (ee 94-98%) in yields of 43-83% with retention of configuration. The enantiomeric excesses were determined by using homochiral (-butyl(phenyl)phosphinothioic acid as chiral solvating agent. VCH Verlaiseesellschaft mbH, 1996.