Experimental and Computational Insights into the Water‐Mediated Decomposition of N ‐Sulfonylhydrazones: A Catalyst‐Free Synthesis of γ‐Keto/Nitrile Sulfones

This work is an example of water‐mediated decomposition of N ‐sulfonylhydrazones used as sulfonyl‐transferring reagents in the selective sulfa‐Michael reaction in the absence of any base or catalyst. A wide range of substituted N ‐sulfonylhydrazones were tested as sources of sulfonyl anions with enones or acrylonitrile, which in turn provided the γ‐ keto/nitrile sulfones in very good yields. Additionally, we have performed a rigorous computational mechanistic study to investigate the role of water which demonstrates the key role of water in the hydrogen abstraction from N ‐tosylhydrazone to initiate the reaction.