Mn(OAc)₃‐Mediated Sulfonylation of Vinyl Azides Resulting in N‐Unsubstituted Enaminosulfones

Abstract

Mn(OAc)3‐mediated sulfonylation of vinyl azides with the use of sodium sulfinates was developed. As a result, N‐enaminosulfones are formed in high yields. The reaction proceeds through the generation of sulfonyl radical, its addition to the double bond of vinyl azide resulting in elimination of N2 molecule and formation of iminyl radical, which is converted on the final step to the desired product. One of the main features of the developed process is application of substoichiometric amount of Mn(OAc)3 due to participation of the generated iminyl radical in the oxidation of the starting sulfinate.

Electrochemical Annulation of ortho‐Alkynylbiphenyls to Fused Sulfenyl Phenanthrenes and Spiro Cyclohexenone Indenes

“…On the other hand, sulfur‐containing organic compounds are known to exhibit significant biological activities, including anti‐cancer, anti‐obesity, anti‐inflammatory, nematicidal, and anti‐oxidant activities, and have a considerable impact on food and agriculture; also, these structural motifs present in a wide range of medications, [29] organic semiconductors, [30] drugs [31] and natural products [32] . As a result, a reasonable number of synthetic methods and strategies have been established to construct a C‐S bond and produce useful organosulfides [33–37] . In this context, transition metal‐catalyzed cross‐coupling processes are among the popular methods for constructing organosulfides.…”

Decatungstate-Catalyzed Photochemical Synthesis of Enaminones from Vinyl Azides and Aldehydes

“…As a continuation of our studies of the addition of radicals to vinyl azides, − we decided to study how these compounds behave under visible light irradiation in the presence of TBADT. The main feature of vinyl azides is that the addition of radical species to the terminal carbon atom of their CC bond leads to the release of N 2 and the formation of iminyl radicals. − The latter can be further transformed into enamines ,,,− or ketones − or can be subjected to intramolecular cyclization − or homocoupling and heterocoupling. ,, Electrochemical and Cu-catalyzed hydroacylation of vinyl azides via decarboxylative generation of acyl radical from α-ketoacids was also reported.…”