Photoinduced Radical Desulfurative C(sp3)-C(sp2) Coupling via Electron Donor-Acceptor Complexes.

Herein, we disclose a radical desulfurative C-C coupling protocol for the synthesis of 4-alkylpyridines. A variety of substituents on both benzyl thiols and 4-cyanopyridines are tolerated. The reaction is carried out under mild and photocatalyst- and transition-metal-free conditions. Preliminary mechanistic studies show that an electron donor-acceptor complex is formed between benzyl thiols and 4-cyanopyridines under alkaline conditions. Then, a variety of 1°, 2°, and 3° C(sp3)-centered radicals was formed by cleavage of the C-S bond, and the 4-alkylpyridines were achieved through a radical-radical coupling with the pyridyl radical anion.

Visible-Light-Induced Oxidation/[3 + 2] Cycloaddition/Oxidative Aromatization to Construct Benzo[a]carbazoles from 1,2,3,4-Tetrahydronaphthalene and Arylhydrazine Hydrochlorides.

An efficient synthesis of benzo[a]carbazoles via visible-light-induced tandem oxidation/[3 + 2] cycloaddition/oxidative aromatization reactions was reported. The benzylic C(sp3)-H of tetrahydronaphthalene was activated through visible-light photoredox catalyst with oxygen as the clean oxidant under mild reaction conditions. This protocol proceeds efficiently with broad substrate scope, and the mechanism study was performed.

Copper-catalyzed aerobic oxidative coupling of aromatic alcohols and acetonitrile to ß-ketonitriles.

A practical, convenient, and cheap copper-catalyzed aerobic oxidative coupling of aromatic alcohols and acetonitrile to ß-ketonitriles has been developed. The green C-C bond formation involving the loss of two hydrogen atoms from the corresponding two carbons, respectively, unlocks opportunities for markedly different synthetic strategies.

Formation of C=N bonds by the release of H2: a new strategy for synthesis of imines and benzazoles.

A new strategy for synthesis of imines using the approach of release of H2 has been developed. This oxidant- and acceptor-free Pd/C catalysis protocol is further applied to synthesis of benzoxazoles, benzimidazoles, and benzothiazoles through a one-pot cascade reaction with notably high yields.

Dioxygen in combination with hydrazine: a practical system for degradation of a broad spectrum of toxic organics in water.

Green and cost-effective eradication of pollutants from water is an important and long-standing goal in environmental chemistry. A broad spectrum of toxic organics in water was efficiently destroyed in the presence of dioxygen in combination with hydrazine hydrate at 150 °C. Under this operating condition, two typical classes of toxic organic chemicals, phenols and nitrobenzene derivatives were totally destroyed. The mineralization rate of these organics was 35-86%. Furthermore, when this degradation system was applied to degradation of actual waste water of wood pulp bleaching with chlorine (COD: 1830 mg/L), 77% COD decrease and 52% TOC mineralization of the wastewater were observed. In each case, the major degradation products are small molecular compounds, such as methanol, formic acid and acetic acid except CO/CO(2). In the case of chlorophenols degradation, no dioxins and any other toxic compounds are detected by (1)H NMR. After degradation reaction, the hydrazine was also decomposed into N(2) and H(2)O, and no remaining hydrazine is found.