What is it about?
Nitrogen-containing compounds such as azoles and anilines are important building blocks in pharmaceuticals, agrochemicals, and materials. In this study, we discovered that 1-chlorovinyl p-tolyl sulfoxides react with metal amides through an unusual cine-substitution process, in which the incoming nitrogen group is introduced at a position adjacent to the leaving group rather than replacing it directly. This reaction provides β-enamino sulfoxides in high yields from a wide range of nitrogen nucleophiles. We also developed a simple desulfinylation step that converts these intermediates into N-vinyl azoles and N-vinyl anilines. Mechanistic experiments and DFT calculations revealed that the transformation proceeds through a β-elimination–addition pathway rather than a direct substitution process.
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Why is it important?
Direct formation of carbon–nitrogen bonds on vinyl systems is an important challenge in synthetic chemistry. This work introduces a new and efficient strategy for preparing β-enamino sulfoxides and N-vinyl nitrogen heterocycles from readily accessible 1-chlorovinyl p-tolyl sulfoxides. The reaction expands the synthetic utility of vinyl sulfoxides and demonstrates a rare example of cine-substitution involving nitrogen nucleophiles. In addition, the combination of cine-substitution and desulfinylation provides access to N-vinyl products that are structural isomers of compounds obtained through previously known SNV reactions of magnesium alkylidene carbenoids. The mechanistic insights obtained from experimental and computational studies also improve our understanding of nucleophilic substitution processes in activated vinyl systems.
Perspectives
This work grew out of our long-standing interest in the chemistry of 1-chlorovinyl p-tolyl sulfoxides and the unusual reactivity of these compounds. During our investigation of reactions with nitrogen nucleophiles, we encountered a transformation that could not be explained by the substitution pathways we initially expected. Exploring this unexpected result led us to the discovery of an efficient cine-substitution reaction and to a deeper mechanistic understanding of the process. I am particularly pleased that this study not only provides a practical method for N-vinylation but also reveals how changing the order of reagent addition can lead to different classes of products from the same starting materials. I hope this work encourages further exploration of vinyl sulfoxide chemistry and inspires the discovery of other unconventional substitution reactions.
Associate Professor Tsutomu Kimura
Read the Original
This page is a summary of: Synthesis of β‐Enamino Sulfoxides via
Cine
‐Substitution of 1‐Chlorovinyl
p
‐Tolyl Sulfoxides with Lithium Amides, Advanced Synthesis & Catalysis, June 2026, Wiley,
DOI: 10.1002/adsc.70584.
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