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Substitution‐ and Elimination‐Free Phosphorylation of Functionalized Alcohols Catalyzed by Oxidomolybdenum Tetrachloride
Author(s) -
Liu ChengYuan,
Pawar Vijay D.,
Kao JunQi,
Chen ChienTien
Publication year - 2010
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200900279
Subject(s) - chemistry , triethylamine , allylic rearrangement , catalysis , ether , medicinal chemistry , organic chemistry , adduct , substitution reaction , ethanol
Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl 4 ) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et 3 N). 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, 1 H, and 31 P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride‐triethylamine adduct such as [(RO)Mo(O)Cl 3 ‐Et 3 N] to be responsible for the catalytic turnover.