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Synthesis of ortho esters

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Primary, secondary and electron-deficient tertiary alcohols react rapidly with ketene dimethyl acetal to form mixed ortho esters, without catalysts and under solvent-free conditions. 1,2-Diols yield bis(mixed ortho esters), rather than cyclic ortho esters.
K. L. Cosgrove, R. P. McGeary, Synlett, 2008, 2425-2428.


Bicyclo orthoesters and amide acetals were prepared from the corresponding triols or diethanolamines using α,α-difluoroalkylamines. The reactions proceeded under mild conditions.
S. Tange, T. Fukuhara, S. Hara, Synthesis, 2008, 3219-3222.