Visible-Light-Mediated Synthesis of Thio-Functionalized Pyrroles.

We have developed an electrochemical approach for the synthesis of fully substituted 1,2,3-thiadiazoles from α-phenylhydrazones at room temperature, which is very challenging and complementary to the conventional thermal reactions. The key step involves anodic oxidation of phenylhydrazone derivatives at a constant current followed by N,S-heterocyclization. The protocol is remarkable in that it is free of a base and free of an external oxidant and can be converted to a gram scale for postsynthetic drug development with functional thiadiazoles. Most importantly, the electrochemical transformation reflected efficient electro-oxidation with an operationally friendly easy procedure with ample functional molecules. Cyclic voltammograms support the mechanism of this electro-oxidative cyclization process.

Electrochemical Synthesis of 1,2,3-Thiadiazoles from α-Phenylhydrazones.

A concise and practical one-pot sustainable approach for expedient synthesis of 2-arylimino-2H-chromenes by two-component cascade [4 + 2] annulative coupling of easily available 2-hydroxybenzaldehydes with β-ketothioamides has been developed in good yields for the first time. Remarkably, metal- and additive-free conditions, use of simple K2CO3 as a mild base, open atmosphere, exclusive regioselectivity, step/atom economy, nonhazardous reagents, and easy purification are added characteristics to the strategy. This annulative protocol will not only provide an efficient method to access diverse chromene scaffolds, but also enrich the research domain of β-ketothioamides.

Metal-Free One-Pot Annulative Coupling of 2-Hydroxybenzaldehydes with β-Ketothioamides: Access to Diverse 2-Arylimino-2H-Chromenes.

The same δ-acetoxy allenoates and thioamides, under DABCO, pyridine, or tetra-n-butyl ammonium bromide (TBAB) catalysis, undergo distinctly different annulations giving chemoselective routes to dihydrothiophene, thiopyran, or thiazole motifs. Thus, using pyridine in [3 + 2] annulation, dihydrothiophenes are obtained as essentially single diastereomers. By contrast, under DABCO catalysis, allenoates deliver thiopyran motifs in good to high yields through 6-exo-dig cyclization. In the thiazole forming [3 + 2] annulation, tetra-n-butyl ammonium bromide (TBAB) facilitates addition-elimination and 5-exo-trig cyclization in which β- and γ-carbons of allenoates participate to deliver thiazole cores exclusively with a Z-isomeric exocyclic double bond. A possible rationale for these observations is delved into.

Priya Saha

Papers

Photo-oxidative Ruthenium(II)-Catalyzed Formal [3 + 2] Heterocyclization of Thioamides to Thiadiazoles.

Electrochemical Synthesis of 1,2,3-Thiadiazoles from α-Phenylhydrazones.

One-pot Mitsunobu Protocol to Access Ketene S,S-/N,S-Acetals at Room Temperature