Achmatowicz Rearrangement Derived Synthons, and their Relevant Bioinspired Chemistry
Pp. 41-98 (58)
Among enormous wealth of natural product structural diversity, those
containing pyran rings are quite common, since they abound in a pool of primary
metabolites as well as among products of sugar transfer biocatalytic processes, which
lead to glycosides and glycoconjugates classified as secondary metabolites.
Additionally, practically every major biogenetic pathway allows, and often promotes,
formation of oxygen heterocycles from polyketides or multiply hydroxylated chain
intermediates, by way of 1,5-diol dehydration, lactonization, intramolecular hydroxyl
group Michael addition, or an intramolecular epoxide ring opening. A variety of the
resulting structures among natural products, which are of interest as prospective leads
for medicinal compounds, elicit problems with the substance availability and call for
efficient synthetic methods of their preparation. The chapter focuses on a particular
rearrangement, featuring ring enlargement of 2-furyl carbinols into pyran-2,3-en- 4-
uloses [2H-pyran-3(6H)-ones], known as Achmatowicz rearrangement (Achmatowicz
reaction; AR), presenting examples of its scope, utility and efficiency, including
remarkable capability for enantioselection in chemo- and biocatalytic preparative
procedures. The rearrangement can constitute the key transformation in stepwise
syntheses of a variety of O- and N- heterocyclic natural products and their mimics,
while its primary products – the unsaturated pyranosuloses, provide versatile
glycosylation synthons which practically do not require protecting groups and secure
easy access to simple and structurally modified mono- and oligo-saccharides with
chosen functions and configurations.
2-Furylcarbinols, Achmatowicz rearrangement, Chemistry,
Dihydropyrans, Enantioselective syntheses of substituted pyrans, Furan oxidative
ring enlargement, Oxygen heterocycles, Palladium catalyzed glycosylation,
Pyranoses, Pyranosuloses, Pyrans, Pyran containing natural products, Structurally
modified saccharides, Tetrahydropyrans, Total synthesis of naturally occurring
pyrans, Unsaturated pyranoses.
Pharmaceutical Research Institute, Warsaw, Poland.