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42.16.1.1.15.2.2 Variation 2: Phosphorylation with (2-Oxo-5,5-diphenyloxazolidin-3-yl)phosphonates

DOI: 10.1055/sos-SD-042-00920

McKenna, C. E.; Kashemirov, B. A.; Błażewska, K. M.Science of Synthesis, (200942829.

Diethyl or diphenyl (2-oxo-5,5-diphenyloxazolidin-3-yl)phosphonate 147 (R2=Et, Ph), readily obtained from 5,5-diphenyloxazolidin-2-one by reaction with the corresponding phosphorochloridate,[‌128‌] can be used in the synthesis of phosphate triesters 149 (Scheme 47).[‌127‌,‌128‌] The reagents react either in the presence of butyllithium or in the presence of a copper(II) trifluoromethanesulfonate catalyst, triethylamine, and N,N-bis[(E)-benzylidene]ethane-1,2-diamine (148, BEN), a chelating ligand. In both cases, the reaction proceeds well with primary, secondary, and, in contrast to diphenyl phosphorochloridate, tertiary alcohols 146, as well as with phenols. The butyllithium-based protocol appears to be more efficient for the synthesis of phosphate triesters from diethyl (2-oxo-5,5-diphenyloxazolidin-3-yl)phosphonate (4497%), whereas the copper(II) trifluoromethanesulfonate system is preferable for reactions with diphenyl (2-oxo-5,5-diphenyloxazolidin-3-yl)phosphonate (4688%).[‌128‌] Lewis acid catalysis is comparatively mild and is therefore applicable to phosphorylation of some sensitive substrates. The copper(II) trifluoromethanesulfonate catalyzed phosphorylation of adenosine and guanosine leads to 5-phosphorylated products that are hydrolyzed to give diesters during purification on a silica gel column (water/methanol elution).

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