An efficient protocol is reported for the synthesis of thioesters from carboxylic acids with use of acyloxy phosphonium salts as intermediates and benzyltriethylammonium tetrathiomolybdate as the sulfur transfer reagent.
Direct synthesis of unsymmetrical beta-sulfonamido disulfides by ring-opening of aziridines by using benzyltriethyl-ammonium tetrathiomolybdate 1 as a sulfur transfer reagent in the presence of symmetrical disulfides as thiol equivalents has been reported. Reaction of benzyl and alkyl disulfides gave unsymmetrical beta-sulfonamido disulfides as the only product in very good yields. From the study, it has been observed that aryl disulfides containing p-NO(2), p-Cl, and p-CN led to the formation of the corresponding beta-aminosulfides as the exclusive products. However, unsubstituted aryl disulfides and the one containing electron-donating substituents (p-Me) provide a mixture of beta-sulfonamido mono- and disulfides as the products.
A new and simple route for the synthesis of thioesters starting from carboxylic acids and alcohols is reported by using tetrathiomolybdate as the key sulfur transfer reagent. Triphenylphosphane and N-bromosuccinimide were used for the activation of the carboxylic acid and alcohol in the same pot followed by the transfer of sulfur from tetrathiomolybdate. Thioesters were obtained in good to moderate yields. Pri-
The thermal reactions of cationic 3d transition‐metal hydrides MH+ (M=Sc–Zn, except V and Cu) with ammonia have been studied by gas‐phase experiments and computational methods. There are three primary reaction channels: 1) H2 elimination by NH bond activation, 2) ligand exchange under the formation of M(NH3)+, and 3) proton transfer to yield NH4+. Computational studies of these three reaction channels have been performed for the couples MH+/NH3 (M=Sc–Zn) to elucidate mechanistic aspects and characteristic reaction patterns of the first row. For NH activation, σ‐bond metathesis was found to be operative.
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