The Dihydroxyacetone Unit—A Versatile C₃Building Block in Organic Synthesis

Abstract

Nature employs dihydroxyacetone phosphate (DHAP) as the donor component in various enzyme-catalyzed aldol reactions. Probably the most significant example in this regard is photosynthesis, in which D-glucose, the most widespread natural product, is formed in just a few steps from DHAP. In recent years a number of synthetic equivalents of DHAP have been reported that deserve particular attention, as their applicability in organic synthesis is not limited to (stereoselective) aldol reactions. The power of these reagents has also been demonstrated convincingly in numerous other asymmetric electrophilic alpha-substitution reactions in target-oriented syntheses. Furthermore, the related 1,3-dioxins are useful equivalents of 2-substituted acrolein derivatives.

Immobilizing Systems Biocatalysis for the Selective Oxidation of Glycerol Coupled to In Situ Cofactor Recycling and Hydrogen Peroxide Elimination

“…[15,16] DHA synthesis catalyzed by isolated glycerol dehydrogenase is rather limited by product inhibition suffered by such enzymes. Furthermore, the enzymatic synthesis of DHA requires expensive redox cofactors that burden the industrial application of this biotransformation.…”

The First Mimetic of the Transketolase Reaction

“…five-step synthetic approach to aromatic and aliphatic dihydroxy ketones starting from 1,4-dioxene and lithiation with tert-butyllithium, [4] a strategy including a ruthenium-catalyzed oxidation of allenes, [5] a double hydroxylation of silyl enol ethers with m-chloroperbenzoic acid, [6] the utilisation of 1-chloroalkyl p-tolyl sulfoxides as hydroxycarbonyl anion equivalents, [7] the approach by Enders et al to enantiomeric α,αЈ-dihydroxy ketones using dihydroxyacetone and chiral auxiliaries, [8] and an organoiron-templated route to cyclic species. [9] The lack of concise, direct strategies, presumably stems from the difficulties associated with creating a stable hydroxycarbonyl anion equivalent: umpolung approaches using dithianes or tert-butyl hydrazones can result in β-elimination of hydroxide or alkoxide upon generation of the hydroxycarbonyl anion.…”

Production of dihydroxyacetone from an aqueous solution of glycerol in the reaction catalyzed by an immobilized cell preparation of acetic acid bacteria Gluconobacter oxydans ATCC 621

“…The dihydroxyacetone (DHA) has various uses in cosmetics [5,10,16,31], medicine [8,17,30], pharmaceuticals [12] and food industries [24,26,34]. Its production from glycerol is financial interesting due to the overproduction of glycerol by the biodiesel industry.…”