New routes towards azomethine ylide generation from prolines to synthesize diverse -heterocycles: a DFT supported -selective mechanism.

Azomethine ylides are generated using either organocatalysts or metal catalysts a ballet of decarboxylative C-N coupling choreographed by prolines. These strategies enable diastereoselective [3 + 2] cycloaddition, C-C coupling, and ring annulation, providing sustainable routes. The synthesized pyrrolizines and other heterocycles have potential applications in the development of crucial biomolecules and pharmaceuticals.

Ring expansion and fused cyclization catalysis to construct indoloquinazolinones with functionalization.

In this study, a straightforward, moisture insensitive, and regioselective Fe-Cu/-TSA-Cu catalyzed reaction is achieved from readily available isatin and 2-alkynylaniline to furnish diverse 12-benzoyl/benzyl/alkyl indolo[1,2-]quinazolin-6(5)-ones. This catalytic method includes C-C cleavage, multi bond forming ring expansion, fused-ring construction, broad substrate scope, gram-scale producibility, and high atom economy.

Catalytic I-moist DMSO-mediated synthesis of valuable α-amidohydroxyketones and unsymmetrical -bisamides from benzimidates.

We developed an efficient and straightforward I-catalyzed strategy for the synthesis of functionalized α-amidohydroxyketones and symmetrical and unsymmetrical bisamides using incipient benzimidate scaffolds as starting materials and moist-DMSO as a reagent and solvent. The developed method proceeds through chemoselective intermolecular N-C-bond formation of benzimidates and the α-C(sp)-H bond of acetophenone moieties. The key advantages of these design approaches include broad substrate scope and moderate yields.

A competitive and highly selective 7-, 6- and 5-annulation with 1,3-migration through C-H and N-H - alkyne coupling.

We demonstrated a highly competitive and selective C-C and N-C cross-coupled 7-, 6- and 5-annulation utilizing 2-ethynylanilides to afford functionalized 1H-benzo[b]azepin-2(5H)-ones, 2-quinolinones, and 3-acylindoles in high yield. ZnCl2 was found to be the smart catalyst for 7- and 5-annulation with 1,3-migration through C-H and N-H functionalization, respectively, whereas molecular iodine performed the C-H functionalized 6-annulation with a nonconventional 1,3 H-shift. The mechanism was investigated by intermediate trapping, control, and labeling experiments.

Selective amidation by a photocatalyzed umpolung reaction.

A metal-catalyzed organic transformation merged with another organophotocatalyst has been developed under mild conditions for production of α-ketoamides. CuI-catalyzed highly selective and rapid COCH-amidation in the presence of electrophilic C[double bond, length as m-dash]O bonds, which is synchronized by an eosin Y (EY)-photocatalyst, furnishes a wide range of labile α-ketoamides, unsymmetrical oxalamides and chiral analogues on the treatment of 1,3-dicarbonyls with amines, PhIO and LED light at room temperature. The current strategy opens up a new avenue to making photocatalysis a common synthetic tool for large-scale production in academia and industry.

Composition-dependent nanoelectronics of amido-phenazines: non-volatile RRAM and WORM memory devices.

A metal-free three component cyclization reaction with amidation is devised for direct synthesis of DFT-designed amido-phenazine derivative bearing noncovalent gluing interactions to fabricate organic nanomaterials. Composition-dependent organic nanoelectronics for nonvolatile memory devices are discovered using mixed phenazine-stearic acid (SA) nanomaterials. We discovered simultaneous two different types of nonmagnetic and non-moisture sensitive switching resistance properties of fabricated devices utilizing mixed organic nanomaterials: (a) sample-1(8:SA = 1:3) is initially off, turning on at a threshold, but it does not turn off again with the application of any voltage, and (b) sample-2 (8:SA = 3:1) is initially off, turning on at a sharp threshold and off again by reversing the polarity.

General base-tuned unorthodox synthesis of amides and ketoesters with water.

We discovered a highly reactive λ(3)-hypervalent iodane species using an inorganic/organic base for the unorthodox synthesis of amides and ketoesters through grafting terminal alkynes. In contrast to the metal-catalyzed dehydrative approaches the in situ generated nonmetallic reagent efficiently created C-N/C-O and C[double bond, length as m-dash]O bonds with amines/alkynes and water at rt.

Ni(II)-salt catalyzed activation of primary amine-sp(3)Cα-H and cyclization with 1,2-diketone to tetrasubstituted imidazoles.

NiCl2·6H2O and Ni(OAc)2·4H2O were found as efficient catalysts for C-H activation of benzyl and aliphatic amines for an unprecedented multi C-N bond forming cyclization with 1,2-diketones under refluxing toluene to furnish highly substituted and polycyclic imidazoles.

Synthetically useful noncatalytic strategy: a stereocontrolled rapid cyclization of a three component system to afford hexahydropyrrolizines.

We demonstrate a highly regio- and stereoselective annulation strategy involving unprecedented C2-H and N-H of proline esters, α,β-unsaturated aromatic aldehydes and deactivated olefins without a catalytic aid to afford medicinally important pyrrolo[3,4-a]pyrrolizines and hexahydropyrrolizines under benign reaction conditions.