A concise and efficacious benzotriazole-mediated novel two-step protocol has been developed for easy access to glycoconjugate benzothiazoles from protected carbohydrates. The benzotriazolemethanethione 3, prepared by the reaction of free alcohol with bis(1H-benzo[1,2,3]triazol-1-yl)methanethione, on treatment with silanes or stannane under heating or microwave irradiation undergoes free radical β-scission of N-N bond and affords diverse range of 2-O-substituted benzothiazoles 4 via cyclative elimination of molecular nitrogen. The structures of all of the compounds have been elucidated using IR, NMR, MS, and elemental analysis, and five of them have been characterized by single-crystal X-ray analysis.
We report herein the facile synthesis and structural characterization of a highly stable dinuclear Cu(i) complex, [(PPh)Cu(μ-tda)Cu(PPh)]·6HO 1 (tda = thiodiacetate anion), in which the Cu-Cu distance is 7.197 Å. This "pre-formed" complex serves as an extremely efficient and recyclable homogeneous catalyst (2 mol%, 30 min) for CuAAC in dichloromethane solvent. The synthesis of a variety of glycoconjugates under ambient conditions is successfully achieved using 1 as a catalyst. The products are obtained in high yields and very short reaction times while complying with the "click protocols". A simpler procedure solely involving the mixing of substrates with 1 (i.e. base free and solvent free) gave the corresponding glycoconjugate in 10 min using 2 mol% of the catalyst.
Newly synthesized Cu(i) with thiobenzoate complexes was found to catalyse the regioselective synthesis of glycoconjugate triazoles under click reaction.
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