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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
Author(s) -
Hammerschmidt Friedrich,
Schmidt Susanne
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961291217
Subject(s) - chemistry , phosphonate , deprotonation , substituent , enantiomer , phosphate , medicinal chemistry , optically active , ether , enantiomeric excess , carbanion , walden inversion , organic chemistry , stereochemistry , enantioselective synthesis , catalysis , ion
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.