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Metallation of Phosphorylated Aliphatic Alcohols to Configurationally Stable α‐Oxyalkyllithium Compounds − Use of the Phosphoryl Group as an Activating Group and Electrophile
Author(s) -
Hammerschmidt Friedrich,
Schmidt Susanne
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200006)2000:12<2239::aid-ejoc2239>3.0.co;2-v
Subject(s) - chemistry , isopropyl , regioselectivity , steric effects , phosphonate , electrophile , deprotonation , alkyl , medicinal chemistry , stereochemistry , electrophilic aromatic substitution , electrophilic substitution , group (periodic table) , metalation , organic chemistry , catalysis , ion
Alkyl diisopropyl phosphates were metallated by s BuLi/TMEDA at −78 °C at the alkyl and isopropyl group in a ratio which is strongly influenced by steric effects. The regioselectivity of deprotonation was very high by use of heptadeuterioisopropyl groups, which reflects a high primary kinetic isotope effect ( k H / k D ⩾ 100). The dipole‐stabilized, phosphoryloxy‐substituted alkyllithium compounds formed are configurationally stable and rearrange with retention of configuration (phosphate−phosphonate rearrangement).