Substitution‐ and Elimination‐Free Phosphorylation of Functionalized Alcohols Catalyzed by Oxidomolybdenum Tetrachloride

Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl₄) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et₃N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution‐free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert‐butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution‐free phosphorylations of 1‐phenylethanol and 1‐(2‐naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI‐MS, IR, ¹H, and ³¹P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride‐triethylamine adduct such as (RO)Mo(O)Cl₃‐Et₃N] to be responsible for the catalytic turnover.