Sustainable Synthesis of Indole-Substituted Densely Functionalized Pyrrole.

A novel chromatography- and catalyst-free methodology has been developed for the synthesis of poly substituted pyrrole in good yields via a multicomponent reaction of arylglyoxal, 1,3-dicarbonyl, indole, and aromatic amine. This strategy provides various advantages such as simple experimental and workup procedures, mild reaction conditions, no added catalyst, use of green solvent, and simple purification procedure of pure product without using column chromatography. This green method offers a simple and highly effective strategy to synthesize a wide range of indole-pyrrole conjugates in a one-pot operation.

The thiocarbonyl 'S' is softer than thiolate 'S': a catalyst-free one-pot synthesis of isothiocyanates in water.

Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS(-).Et(3)NH(+)) with methyl acrylate in an aqueous medium gave solely arylisothiocyanate (ArNCS), whereas the in situ generated aryl dithiocarbamic acid (ArNHCSS(-).H(+)) yielded exclusively the thia-Michael adduct (ArNHCSSCH(2)CH(2)COOMe).

Hypervalent iodine(III)-mediated oxidation of aldoximes to N-acetoxy or N-hydroxy amides.

Treatment of various aliphatic and aromatic aldoximes with the hypervalent iodine(iii) reagents (diacetoxyiodo)benzene (DIB) or Koser's reagent [hydroxy(tosyloxy)iodo]benzene (HTIB) gave, respectively, N-acetoxy or N-hydroxy amides in good yields rather than the expected nitrile oxide dimerised product oxadiazole-N-oxides reported to be formed with other oxidising and hypervalent iodine reagents. The acetate or the hydroxyl group of DIB or HTIB attacks on the aryl/alkylnitrile oxides formed in situ, which, upon intramolecular rearrangement, gave the expected N-acetoxy or N-hydroxy amides.

Intra- and intermolecular C-S bond formation using a single catalytic system: first direct access to arylthiobenzothiazoles.

We have for the first time developed two ligand-assisted Cu(I)-catalyzed sequential intra- and intermolecular S-arylations leading to the direct synthesis of arylthiobenzothiazoles in one pot without an inert atmosphere. Low catalyst loading, inexpensive metal catalyst and ligand, lower reaction temperature, and shorter reaction times make this method superior to all reported methods for the synthesis of arylthiobenzothiazole.

Hypervalent iodine(III)-mediated regioselective N-acylation of 1,3-disubstituted thioureas.

Reaction of asymmetrical 1,3-disubstituted thioureas with diacetoxyiodobenzene (DIB) produces regioselectively N-acetylurea in shorter time. Regioselectivity is dependent on the pKa's of the amine attached to the thiourea moiety with acylation taking place toward the amine having a lower pKa. This is the first example of DIB being employed as an N-acetylating agent.