Palladium-Catalyzed Carbonylation of Azides and Mechanistic Studies

Isocyanates are widely applied in the fields of materials science, drug discovery and chemical industry processes. Palladium-catalyzed carbonylation of azides with carbon monoxide (CO) is reported as a powerful method for simple and efficient access to isocyanates, which are important precursors for preparing structurally meaningful urea, carbamate and amidine derivatives. In this account, we provide an overview on the synthesis of isocyanates and their subsequent reactions to obtain diverse nucleophilic addition products. In addition, with particular emphasis on our mechanistic studies of the Pd-catalyzed carbonylation process, we outline the identification of the actual catalytic species, the possible intermediates and some key factors in the catalytic cycle.1 Introduction2 Palladium-Catalyzed Reaction of Azides with CO and Subsequent Nucleophilic Additions3 Mechanistic Studies on the Palladium-Catalyzed Reaction of Azides with CO3.1 Studies on the Actual Catalytic Species and the Key Intermediates in the Activation and Carbonylation of Acyl Azides3.2 Study of the Sulfonylurea Product Self-Catalyzed Carbonylation of Sulfonyl Azides3.3 Study of the Actual Catalytic Pattern of the Pd/C Catalyst4 Conclusion

Synthesis of N-methylated amines from acyl azides using methanol

The Ru(ii) complex catalysed direct transformation of acyl azides into N-methylamines was developed for the first time using methanol via the one-pot Curtius rearrangement and borrowing hydrogen methodology.

Acyl azide generation and amide bond formation in continuous-flow for the synthesis of peptides

Acyl azides were safely generated by using nitrous acid in water and reacted in situ within a flow system. The acyl azide was efficiently extracted into the organic phase containing an amine nucleophile for a highly enantioselective peptide coupling.

A Facile and Efficient Approach for the Synthesis of 3-Aryl-4-hydroxy-1,3-thiazolidin-2-ones

A facile and efficient method for the synthesis of 3-aryl-4-hydroxy-1,3-thiazolidin-2-ones by the reaction of 1,4-dithiane-2,5-diol with acyl azides is reported. This reaction proceeded well at 80 °C to afford products in excellent yields for a wide range of substrates. A possible mechanism has been proposed.