Investigation and Application of Amphoteric α-Amino Aldehyde: An in Situ Generated Species Based on Heyns Rearrangement

Abstract

In situ generation of the reactive amphoteric α-amino aldehyde with simple α-hydroxy ketones and phenylamine via Heyns rearrangement was proven to be feasible. Metal-free domino reactions based on this reactive intermediate were effectively used to afford important N-heterocycles including polysubstituted pyrroles, indoles, and quinoxalines conveniently. A simple starting material, water as the only byproduct, and diversity of the useful products will make this method greatly attractive for pharmaceutics.

Green Hydrothermal Synthesis of Fluorescent 2,3‐Diarylquinoxalines and Large‐Scale Computational Comparison to Existing Alternatives

“…Quinoxalines are widely used in medicine, for example, as antibacterial, antifungal, or anticancer agents, [3–5] and also as building blocks in advanced materials [6–8] . Various syntheses of quinoxalines have been reported, most employing 1,2‐diamines in combination with different carbonyl compounds (Scheme 1B), that is, mainly diketones or α‐substituted carbonyl compounds (e. g., α‐hydroxyketones, [9–12] α‐bromoketones [13] or α‐oximeketones [14] ), and the transformations require the presence of oxidizing agents. The vast majority of reported syntheses of quinoxalines use traditional organic solvents and require reaction times ( t r ) of several hours.…”

Catalytic asymmetric synthesis of N-substituted tetrahydroquinoxalines via regioselective Heyns rearrangement and stereoselective transfer hydrogenation in one pot

“… 9 Due to the significance of the reaction as well as the importance of the corresponding products, our group has paid much attention to its application. 10 Recently, we investigated the production and application of the in situ formed α-amino aldehyde intermediate and synthesized different N-heterocycles by using different types of nucleophiles. 10 a…”

The synthesis ofN‐containing heterocyclic compounds catalyzed by copper/L‐proline

“…[ 5 ] Tandem reaction possessing the advantages of quickly preparing complex molecules from common starting materials in one single operation without isolating intermediates, has been paid more and more attention. [ 6 ] Therefore, copper‐catalyzed tandem reactions have become a power tool for the construction of N ‐containing heterocyclic motif. [ 7 ] Generally speaking, single copper served as the catalyst is not active, but adding ligand to copper catalyst can enhance the catalytic efficiency.…”