Synthesis of five- and six-membered heterocycles by dimethyl carbonate with catalytic amounts of nitrogen bicyclic bases?

Green Chemistry Pub Date: 2014-11-11 DOI: 10.1039/C4GC01822B

Abstract

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 BAc2 mechanism are herein used for the first time as efficient catalysts for cyclization reactions encompassing both BAc2 and BAl2 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.

Graphical abstract: Synthesis of five- and six-membered heterocycles by dimethyl carbonate with catalytic amounts of nitrogen bicyclic bases
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