A novel product-derived bimetallic palladium complex catalyzes a sulfonylazide-transfer reaction with the σ-donor/π-acceptor ligand CO, and is advantageous given its broad substrate scope, high efficiency, and mild reaction conditions (atmospheric pressure of CO at room temperature). This methodology provides a new approach to sulfonylureas, which are present in both pharmaceuticals and agrochemicals. The synthesis of Glibenclamide on a gram scale further revealed the practical utility of this procedure. Mechanistically, the generation of a bridged bimetallic palladium species derived from the product sulfonylurea is disclosed as the crucial step for this catalytic cycle.

Anovel product-derived bimetallic palladium complex catalyzesasulfonylazide-transfer reaction with the sdonor/p-acceptor ligand CO,a nd is advantageous given its broad substrate scope,h igh efficiency,a nd mild reaction conditions (atmospheric pressure of CO at room temperature). This methodology provides an ew approach to sulfonylureas, which are present in both pharmaceuticals and agrochemicals. The synthesis of Glibenclamide on ag ram scale further revealed the practical utility of this procedure.Mechanistically, the generation of ab ridged bimetallic palladium species derived from the product sulfonylurea is disclosed as the crucial step for this catalytic cycle.Selective transition-metal-catalyzed C À Nb ond formation via an itrene has attracted considerable attention because of its high synthetic value in the construction of diverse Ncontaining compounds.[1] Ther ecently developed procedure using organic azides as nitrene precursors does not require any external oxidant and releases N 2 as the only byproduct. In particular,c ommercially available and air-stable sulfonylazides have played an important role in achieving the concise synthesis of N-substituted sulfonyl amides.T od ate,t hese transformations are usually catalyzed by Rh, Ir, Ru, Fe,C o, etc., [2] with either noble metals or complicated and sensitive ligands (Scheme 1). In contrast, palladium complexes,w hich serve as common catalysts for various cross-coupling reactions, [3] have rarely been used in the transformation of sulfonylazides.T he palladium-catalyzed coupling reactions between carbenes/nitrenes with s-donor/p-acceptor ligands, however, has grown remarkably in recent years.P alladiumcatalyzed carbene-transfer reactions with CO,a lkynes,a nd isocyanides to form ketenes,allenes,and ketenimines,respectively,h ave been well developed.[4] However,adirect palladium-catalyzed nitrene-transfer strategy with a s-donor/pacceptor ligand, which also represents asynthetically valuable method for introducing nitrogen moiety to unsaturated systems,h as not been well explored.[5] To the best of our knowledge,p alladium-catalyzed carbonylation of sulfonylazides has scarcely been reported. Thus,w eh ave paid much attention to palladium-catalyzed cross-coupling reactions of sulfonylazides with CO,a na pproach which would provide ap otential strategy to access sulfonyl isocyanate,ak ey intermediate to sulfonylurea derivatives.Sulfonylurea derivatives are common structural motifs in pharmaceuticals [6] and agrochemicals. [7] Thet raditional method to access sulfonylureas is the reaction of sulfamides with phenyl carbamates,and it produces much waste.[8] Other approaches include the coupling of either alkyl isocyanates with sulfamides, [9] or sulfonyl isocyanates with amines, [10] both of which require the use of phosgene.Inaddition, the former approach is unsatisfactory because of the weak nucleophilicity of sulfamides,w hereas the latter approach is also limited because of the difficulty in synthesizing sulfonyl isocyanates. An alternative strateg...

A novel Pd‐catalyzed nitrene‐transfer reaction of sulfonylazides with CO is developed which provides a new approach to sulfonylurea derivatives.