Carbenoid and Vinylogous Reactivity of Diazo Arylidene Succinimide (DAS) with Benzyl Aryl Thioethers under Rhodium Catalysis

Dedication

Dedicated to Prof. Srinivasan Chandrasekaran on the occasion of his 80th birthday.

Abstract

Herein, we have explored the reactivity of diazo arylidene succinimide (DAS) with benzyl thioether to achieve [1,2]/[1,4]-Stevens rearrangement via rhodium catalysis. The protocol has successfully demonstrated the substituent-dependent competitive reactivity of DAS to tune the ratio of [1,2]-Stevens and [1,4]-Stevens rearrangement products. The protocol facilitated the formation of C–C and C–S bonds between carbenoid/vinylogous center. This catalytic protocol works smoothly in environmentally benign solvents to afford the corresponding desired products in moderate to good yields. The protocol proved to be scalable on gram quantity.

Keywords

Diazo arylidene succinimides (DAS) - Metal carbenoid - Carbenoid and vinylogous reactivity - Stevens rearrangement - Rhodium catalysis

Publication History

Received: 22 October 2025

Accepted after revision: 25 January 2026

Accepted Manuscript online:
31 January 2026

Article published online:
26 February 2026

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