Abstract Phosphorylation of various aliphatic alcohols gives phosphates 1 which are deprotonated by sBuLi/TMEDA in diethyl ether, THF or hexane at −78 °C. The organo-lithiurns 2 and 4 formed isornerize to α-hydroxy- phosphonates 3 and 5 (phosphate-phosphonate rearrangement[1.2]