This article summarizes the recent developments (particularly the uses of homogeneous organometallic catalysts) in ring-opening carbonylations, ring-opening carbonylative polymerizations and ring-expansion carbonylations of heterocycles such as epoxides, aziridines, lactones and oxazolines.

The regio- and stereoselective ring-opening of a 2-(2'-oxiranyl)-1,2,3,6-tetrahydropyridine using organometallic reagents is reported. The choice of the organometallic reagent determines the formation of either 2-[(R)-1-hydroxyalkyl]- or 2-[(S)-2-hydroxy-1-alkyl]-1,2,3,6-tetrahydropyridines. The formation of 2-[(S)-2-hydroxy-1-alkyl]-1,2,3,6-tetrahydropyridines is a rare example of epoxide ring...

Epoxides and aziridines are common intermediates in synthesis. Readily accessible in enantioenriched form, they are typically used as electrophiles, taking advantage of their predictable highly regioselective ring-opening reactions. Our work in the area of α-lithiated terminal epoxides and aziridines indicates that there are many other less conventional but useful reactions of these small-ring ...

We describe the use of an air-stable iridium hydride catalyst for the isomerization of terminal epoxides into aldehydes with perfect regioselectivity. The system operates at low loadings of catalyst (0.5 mol%), is highly practical, scalable, and tolerates functional groups that would not be compatible with Lewis acids typically used in stoichiometric amounts. Evidence for a rare hydride mechani...

Time for SOme MOre: For the first time SOMO (singly occupied molecular orbital) activation has been exploited to allow a new approach to the alpha-chlorination of aldehydes. This transformation can be readily implemented as part of a linchpin catalysis approach to the enantioselective production of terminal epoxides.

The combination of ultrasound and photochemical methods has been used for the catalytic ring opening of alpha-epoxyketones by 1-benzyl-2,4,6-triphenylpyridinium tetrafluoroborate (NBTPT) as photocatalyst in methanol. Sonication of these compounds in the presence of NBTPT did not result in the opening of epoxide ring, but the use of ultrasound increased the rate of photoreaction.

Enantioselective desymmetrization of meso-aziridines and meso-epoxides with various nucleophiles by organocatalysis has emerged as a cutting-edge approach in recent years. This review summarizes the origin and recent developments of enantioselective desymmetrization of meso-aziridines and meso-epoxides in the presence of organocatalysts.

Starting from commercially available (-)-quinic acid, the enantioselective total syntheses of trichodermamides A and B were achieved. The key reactions involve the stereoselective construction of the oxazine ring via an intramolecular epoxide ring opening reaction and an EDCI-assisted peptide coupling reaction.