A catalytic amount of a nitrogen bicyclic base, i.e., DABCO, DBU or TBD, is effective for the one-pot synthesis of heterocycles from 1,4-, 1,5-diols and 1,4-bifunctional compounds via dimethyl carbonate chemistry under neat conditions. Nitrogen bicyclic bases that were previously shown to have enhanced the reactivity of DMC in methoxycarbonylation reaction by a B(Ac)2 mechanism are herein used for the first time as efficient catalysts for cyclization reactions encompassing both B(Ac)2 and B(Al)2 pathways. This synthesis procedure was also applied to a large scale synthesis of cyclic sugars, isosorbide and isomannide, starting from D-sorbitol and D-mannitol, respectively. The resulting anhydro sugar alcohols were obtained as pure crystalline compounds that did not require any further purification or crystallization.
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