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Greatly Accelerated Condensation of d-Mannose Diacetonide with Aqueous Formaldehyde (Formalin)
Dong-Xing Tan1, Jun You2, Mu-Rong Xu1
1State Key Laboratory of Bioorganic and Natural Products Chemistry, Collective Innovative Center for Chemistry and Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.
Abstract:
Condensation of d-mannose diacetate with aqueous formaldehyde, a long known quaternary center-generating transformation, was reinvestigated to solve the hidden problem of incomplete conversion, a lasting challenge since 1979 despite many previous efforts. The mysterious cause for the retarded transformation was found to be generation of formic acid by a Cannizzaro reaction. By using additional amounts of base, the reaction time was shortened from 48 h to 100 min and the product was readily isolated in 81% yield.
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