Achmatowicz Rearrangement Research Articles

Enantioselective Carbonyl Allylation, Crotylation, and tert-Prenylation of Furan Methanols and Furfurals via Iridium-Catalyzed Transfer Hydrogenation

5-Substituted-2-furan methanols 1a-c are subject to enantioselective carbonyl allylation, crotylation and tert-prenylation upon exposure to allyl acetate, alpha-methyl allyl acetate, or 1,1-dimethylallene in the presence of an ortho-cyclometalated iridium catalyst modified by (R)-Cl,MeO-BIPHEP, (R)-C3-TUNEPHOS, and (R)-C3-SEGPHOS, respectively. In the presence of 2-propanol, but under otherwise identical conditions, the corresponding substituted furfurals 2a-c are converted to identical products of allylation, crotylation, and tert-prenylation. Optically enriched products of carbonyl allylation, crotylation, and reverse prenylation 3b, 4b, and 5b were subjected to Achmatowicz rearrangement to furnish the corresponding gamma-hydroxy-beta-pyrones 6a-c, respectively, with negligible erosion of enantiomeric excess.

Practical, Scalable, High-Throughput Approaches to η3-Pyranyl and η3-Pyridinyl Organometallic Enantiomeric Scaffolds Using the Achmatowicz Reaction

A unified strategy for the high-throughput synthesis of multigram quantities of the eta(3)-oxopyranyl- and eta(3)-oxopyridinylmolybdenum complexes TpMo(CO)(2)(eta(3)-oxopyranyl) and TpMo(CO)(2)(eta(3)-oxopyridinyl) is described (Tp = hydridotrispyrazolylborato). The strategy uses the oxa- and aza-Achmatowicz reaction for the preparation of these organometallic enantiomeric scaffolds, in both racemic and high enantiopurity versions.

De Novo Asymmetric Synthesis of d- and l-Swainsonine

[reaction: see text] The enantioselective syntheses of both enantiomers of the indolizidine natural product swainsonine have been achieved in 13 steps from furan. The indolizidine ring system is installed by a one-pot hydrogenolysis of both an azide and an O-Bn group along with an intramolecular reductive amination reaction. The asymmetry of swainsonine was introduced by Noyori reduction of an acylfuran. This route relies upon an Achmatowicz rearrangement, a diastereoselective palladium-catalyzed glycosylation, Luche reduction, and a dihydroxylation reaction.

Stereocontrolled synthesis of highly functionalised spirocyclic pyrans

Highly functionalized spirocyclic pyrans can be obtained through the Achmatowicz rearrangement of furyl carbinols by taking advantage of the different rates of reaction for epoxidation and nucleophilic addition. Through this methodology, spirocyclic units of various ring sizes can be selectively generated with complete stereocontrol.

A Divergent Synthesis of Uncommon Sugars from Furanaldehyde

A practical synthetic strategy has been developed for producing uncommon sugars. This method employed kinetic enzymatic resolution of 1-(2-furyl)ethanol, and followed by NBS-mediated Achmatowicz rearrangement to construct α,β-unsaturated lactones. After further derivatization, five representative uncommon sugar units were successfully synthesized.