The Phosphonate‐Phosphate‐ and Phosphate‐Phosphonate Rearrangement and Their Applications, 4. Deprotonation of Secondary Benzylic Phosphates — Configurationally Stabile Benzylic Carbanions with a Diethoxyphosphoryloxy Substituent and Their Rearrangement to Optically Active Tertiary α‐Hydroxyphosphonates

Optically active alcohols (ee ≥ 98%) such as 1‐phenylpropanol, 1‐(2‐naphthyl)ethanol, 1‐tetralol, and 1‐indanol were transformed into diethyl phosphates 7a–d . s BuLi/TMEDA — induced phosphate—phosphonate rearrangement in diethyl ether furnished tertiary 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 t ‐butyl(phenyl)phosphinothioic acid as chiral solvating agent.