Photo-Induced Generation of Oxygenated Quaternary Centers via EnT Enabled Singlet O2 Addition to C3-Maleimidated Quinoxaline: A Reagent-Less Approach.

Demonstrated here is an external photo-sensitizer-free (auto-sensitized) singlet oxygen-enabled solvent-dependent tertiary hydroxylation and aryl-alkyl spiro-etherification of C3-maleimidated quinoxalines. Such "reagent-less" photo-oxygenation at Csp3-H and etherification involving Csp3-H/Csp2-H are unparalleled. Possibly, the highly π-conjugated N-H tautomer allows the substrate to get excited by irradiation, and subsequently, it attains the triplet state via ISC. This excited triplet-state sensitized molecule then transfers its energy to a triplet-state oxygen (3O2) generating reactive singlet oxygen (1O2) for hydroxylation and spirocyclization depending on the solvent used. In HFIP, the generated alkoxy radical accepts a proton via HAT giving hydroxylated product. In contrast, in an aprotic PhCl it underwent a radical addition at the ortho-position of the C2 aryl to provide spiro-ether. An unprecedented orthogonal spiro-etherification was observed via the displacement of o-substitutents for ortho (-OEt, -OMe, -F, -Cl, -Br) substituted substrates. The order of ipso substitution follows the trend -OMe>-OEt>-F>-H>-Cl>-Br. Both these oxygenation reactions can be carried out with nearly equal ease using direct sunlight without the requirement of any elaborate reaction setup. Demonstration of large-scale synthesis and a few interesting transformations have also been realized. Furthermore, several insightful control experiments and quantum chemical computations were performed to unravel the mechanism.

Base-Induced Decarboxylative 1,1-Alkoxy Thiolation via Hydrothiolation of Vinylene Carbonate.

A base-mediated 1,1-difunctionalization of vinylene carbonate has been achieved using two different nucleophiles, namely, thiol and alcohol, with the assistance of air (O2). In alcoholic solvents, decarboxylation occurs at room temperature to provide a 1,1-difunctionalized product, where vinylene carbonate serves as an ethynol (C2) synthon in this three-component reaction. On the other hand, in acetonitrile, exclusive hydrothiolation occurs under the basic conditions at room temperature. This method offers a one-pot decarboxylative regioselective difunctionalization of vinylene carbonate at room temperature for the construction of α-alkoxy-ß-hydroxy sulfide.

Copper(I)-Mediated Cascade Annulation via Dual C-H/C-H Activation: Access to Benzo[a]carbazolic AEEgens.

A Cu(I)-mediated cascade cyclization/annulation of unprotected o-alkynylanilines with maleimides in one pot is developed. The protocol offers sequential formation of one C-N and two C-C bonds to deliver fused benzo[a]carbazoles having free NH skeletons. The annulated products display fluorescence emission in the range of 485-502 nm with a large Stokes shift and fluorescence lifetime of ∼17 ns. The annulated 3aa displays AEE behavior in the ethanol/hexane system and possesses marigold-flower-like morphology at the aggregated state. Cell viability assays enumerate biocompatible AEEgens, while their high intracellular fluorescence depicts cell imaging applicability.

Dearomative bis-functionalization of quinoxalines and bis-N-arylation of (benz)imidazoles via Cu(II)-mediated addition of boronic acids.

A Cu(OTf)2-mediated regioselective dearomative aryl-hydroxylation across the C(sp2)N bond of 2-aryl quinoxalines and bis-N-arylation of (benz)imidazoles were developed using aryl boronic acids. For the dearomative aryl-hydroxylation, the C-center should be electrophilic (ca. 0.08), the N-center nucleophilic (ca. -0.50), and the C(sp2)N bond polarized (Δe = 0.609).

Isoxazole as a nitrile synthon: en routes to the ortho-alkenylated isoxazole and benzonitrile with allyl sulfone catalyzed by Ru(II).

A Ru(II) catalyzed regioselective Heck-type C-H olefination of isoxazole with unactivated allyl phenyl sulfone is revealed. The solvent DCM offers dual sp2-sp2 C-H activation via an N-directed strategy, leading to ortho-olefinated isoxazoles with exclusive E-selectivity. On the other hand, in DCE solvent, isoxazole serves as the nitrile synthon and leads to o-olefinated benzonitrile. At a higher temperature (110 °C) in DCE, after the ortho-olefination Ru(II) mediated cleavage of isoxazoles delivered the nitrile functionality.

Mn(I)-Catalyzed Preferential Electrophilic C3-Maleimidation in Quinoxaline Leading to Spirocyclization and Dehydrogenation of Succinimides.

A Mn(I)-catalyzed site-selective nondirected C3-maleimidation of quinoxaline is established. Herein, the electrophilic C3-metalation precedes over the o-directed strategy to access diversely substituted quinoxaline-appended succinimides. The products undergo PIFA-promoted C(sp2)-C(sp3) spirocyclization via π-electrons drifting from aryls and Selectfluor-mediated dehydrogenation of succinimide at room temperature.

Photo-induced 1,2-thiohydroxylation of maleimide involving disulfide and singlet oxygen.

A visible light-driven di-functionalization of maleimide with disulfide and in situ-generated singlet oxygen offers selective 1,2-thiohydroxylation under additive-free conditions. Here the disulfide plays the dual role of photosensitizer and the coupling reagent. Notably, the hydroxyl functionality originates from the in situ generated singlet oxygen followed by HAT from H2O (moisture).

Solvent-Switched Manganese(I)-Catalyzed Regiodivergent Distal vs Proximal C-H Alkylation of Imidazopyridine with Maleimide.

A sustainable Mn(I)-catalyzed exclusive solvent-dependent functionalization of imidazopyridine with maleimide via an electrophilic metalation at the distal (in 2,2,2-trifluoroethanol (TFE)) and chelation assisted at the proximal (in tetrahydrofuran (THF)) has been developed. The strategy was successfully applied to the drug Zolimidine and a broad range of substrates, thereby reflecting the method's versatility.