A practical three-component reaction between unactivated carbohydrates, oxoacetonitriles, and ammonium acetate gave densely functionalized pyrroles in 75−96% yields. Disaccharides afforded novel pyrrolo-glycosides. This metal-free, Et 3 N-catalyzed cascade reaction proceeded with exclusive chemo-, regio-, and stereoselectivities and showed a wide substrate scope with high atom economy. It also proceeded successfully at a 2 g scale, demonstrating potential for large-scale synthesis. The functional groups on the pyrroles permit easy transformation to other handles for the construction of more complex structures. The reaction proceeded through a cascade mechanism involving several intermediates identified by mass spectrometric analysis. This work has great potential for the sustainable production of densely functionalized pyrroles from cheap and widely available carbohydrates and represents a key advancement in the sustainable synthesis of these ubiquitous heterocycles.

Perfluorophenylboronic acid 1c catalyzes the direct stereoselective addition of alcohol nucleophiles to deactivated peracetylated d-galactal 2 to give 2-deoxygalactosides 4a–o, 6a–11a in 55–88% yield with complete α-selectivity.

A convenient protocol was developed for the synthesis of 2,3-unsaturated C-, O-, N- and S-linked glycosides (enosides) using 20 mol % perflurophenylboronic acid catalyst via Ferrier rearrangement. Using this protocol, D-glucals and L-rhamnals reacted with various C-, O-, N- and S-nucleophiles to give a wide range of glycosides in up to 98% yields with mainly α-anomeric selectivity. The perflurophenylboronic acid successfully catalyzed a wide range of substrates (both glucals and nucleophiles) under very mild reaction conditions.

A one-step, three-component reaction between α-hydroxyketones, oxoacetonitriles, and primary amines gives N-substituted 2,3,5-functionalized 3-cyanopyrroles with complete selectivity in up to 90% isolated yields. The reaction worked on a wide substrate scope under mild reaction conditions (AcOH as a catalyst, EtOH, 70 °C, 3 h). The reaction proceeded with very high atom efficiency as water is the only molecule lost during the reaction. The practicality of the reaction was demonstrated on a large gram scale. The structures of the 3-cyanopyrroles were confirmed by single-crystal X-ray diffraction and NMR; this work provides a general and practical entry to pyrrole scaffolds suitably decorated for the synthesis of various bioactive pyrroles in a concise manner.

A simple and concise three-component synthesis of a key pyrrole framework was developed from the reaction between α-hydroxyketones, oxoacetonitriles, and anilines. The synthesis was used to obtain several pyrrole-based drug candidates, including COX-2 selective NSAID, antituberculosis lead candidates BM212, BM521, and BM533, as well as several analogues. This route has potential to obtain diverse libraries of these pyrrole candidates in a concise manner to develop optimum lead compounds.