Journal
ADVANCED SYNTHESIS & CATALYSIS
Volume 352, Issue 1, Pages 188-194Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.200900279
Keywords
catalysis; chemoselectivity; diphenyl phosphates; oxidometallic species; sensitive benzyl phosphates
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Funding
- National Science Council of Taiwan
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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, H-1, and P-31 NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl-3-Et3N] to be responsible for the catalytic turnover.
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