Design and Applications of a SO₂ Surrogate in Palladium‐Catalyzed Direct Aminosulfonylation between Aryl Iodides and Amines

Abstract

A new SO2 surrogate is reported that is cheap, bench‐stable, and can be accessed in just two steps from bulk chemicals. Essentially complete SO2 release is achieved in 5 minutes. Eight established sulfonylation reactions proceeded smoothly by ex situ formation of SO2 by utilizing a two‐chamber system in combination with the SO2 surrogate. Furthermore, we report the first direct aminosulfonylation between aryl iodides and amines. Broad functional group tolerance is demonstrated, and the method is applicable to pharmaceutically relevant substrates, including heterocyclic substrates.

Three‐Component Radical Cross‐Coupling: Asymmetric Vicinal Sulfonyl‐Esterification of Alkenes Involving Sulfur Dioxide

“…In this context, as part of our ongoing efforts on sulfur dioxide insertion reactions, we developed a general and efficient method to achieve asymmetric vicinal sulfonyl‐esterification of alkenes utilizing Cu/PyBim system. [ 14 ] The method encompasses the use of an earth‐abundant metal catalyst, along with mild reaction conditions, a wide range of substrates, and excellent control over enantioselectivity. Notably, this method can be applied to different types of radical precursors, including O ‐acylhydroxylamines, cycloketone oxime esters, aryldiazonium salts, and drug molecules.…”