PdCl2 catalyzed efficient assembly of organic azides, CO, and alcohols under mild conditions: a direct approach to synthesize carbamates

Abstract

A simple and readily available PdCl2 catalyzed carbamate synthesis method via isocyanate generation and application in situ has been developed. This chemistry provides an efficient and practical approach to synthesize carbamates from simple organic azides, CO atmosphere and alcohols. The broad scope, mild and neutral conditions, and only N2 as the byproduct make this transformation very useful. Moreover, simple examples of modification of bioactive molecules and construction of macrocycles were achieved through this protocol.

Norbornene derivatives from a metal-free, strain-promoted cycloaddition reaction: New building blocks for ring-opening metathesis polymerization reactions

“…Mass spectra were measured on an Applied Biosystems QSTAR Pulsar or a Bruker Autoflex II mass spectrometer. Compounds 2–5 were prepared according to literature procedures . Initiator 1 was obtained from Materia and used without further purification.…”

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

“…Thep roduct amide could be obtained by two possible pathways.One is via the isocyanate I derived from am etal nitrene and CO, followed by reaction with arenes.I socyanates have been obtained from azides and CO either under high temperature or by metal catalysis. [17] Theo ther pathway is via the aryl metal intermediate II derived from an arene and metalnitrene,followed by reaction with CO.T his strategy provides as imple catalytic approach to amides from readily available compounds.Herein, we report anovel rhodium-catalyzed CÀ Ha midation to synthesize amides simply from arenes,C O, and organic azides via nitrene intermediates,a nd it provides an efficient strategy for the synthesis of amides from abroad range of substrates (Scheme 1d).…”

Product‐Derived Bimetallic Palladium Complex Catalyzes Direct Carbonylation of Sulfonylazides

“…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. [5] To the best of our knowledge,p alladium-catalyzed carbonylation of sulfonylazides has scarcely been reported. [5] To the best of our knowledge,p alladium-catalyzed carbonylation of sulfonylazides has scarcely been reported.…”