Progress in intermolecular and intramolecular reactions of thioamides with diazo compounds and azides

Abstract

Reactions of thioamides with nitrogen-rich 1,3-dipoles, diazo compounds and azides, have been known for long time already. However in recent years introduction of catalysts of different types (rhodium-, ruthenium-and copper-containing and Lewis acids) as well as highly electrophilic sulfonyl azides, allowed the development of new methods for the synthesis of heterocycles, enamines and N-sulfonyl amidines. Moreover, a new methodology in organic synthesis, based on generation and subsequent transformations of a-diazocarbonyl compounds was created. Reactions of sulfonyl azides with thioamides undergo readily in mild conditions to produce different sorts of N-sulfonyl amidines and represent a new type of click-type processes. Most of the cited works were published in the current decade. Earlier seminal papers are also reviewed when they constitute the background for new synthetic methods which were developed further.

Synthesis of Cyclic Amidines by Iridium-Catalyzed Deoxygenative Reduction of Lactams and Tandem Reaction with Sulfonyl Azides

“…To avoid the use of hazardous reagents and harsh conditions, some other strategies for the synthesis of amidines from amides have been developed. In 2013, Chiba, Hatanaka and co-workers reported a coupling reaction of the amide-derived thioamides and sulfonyl azides for the synthesis sulfonyl amidines, including various cyclic amidines . In 2017, Adolfsson and co-workers developed a reductive functionalization of amides into N -sulfonylformamidines, using Mo­(CO) 6 -catalyzed reduction of amides to enamines as the key step .…”

Reaction of N,N‐Disubstituted Polyfluoroalkanethioamides with Diazomethane: Entry to New Thiirane Derivatives

“…The non-catalyzed reactions between thioamides and diazo compounds are scarce. [21] A few examples of such reactions, which have been reported in the literature, include methylation of aromatic and heterocyclic N-arylthioamides with diazomethane affording S-methylthioimidates in high yields. [22] Cyanothioformanilide was shown to react with diphenyldiazomethane to give the corresponding enamine isolated in 40 % yield.…”

Synthesis and crystal structure of 2-azido-N-(4-nitrophenyl)acetamide, C8H7N5O3

“…Azides have found valuable applications in medicinal chemistry [5], molecular biology [6], and an increasing interest in the field of organic synthesis as intermediates for the preparation of heterocycles such as tetrazoles, triazolines, triazoles, etc. [7][8][9].…”