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Updated: Nov 21, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
[1,3]-Claisen Rearrangement via Removable Functional Group Mediated Radical Stabilization
Md Nirshad Alam1,2, Soumya Ranjan Dash2,3, Anirban Mukherjee1
1Organic Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008, India.
Abstract:
A thermal O-to-C [1,3]-rearrangement of α-hydroxy acid derived enol ethers was achieved under mild conditions. The 2-aminothiophenol protection of carboxylic acids facilitates formation of the [1,3] precursor and its thermal rearrangement via stabilization of a radical intermediate. Experimental and theoretical evidence for dissociative radical pair formation, its captodative stability via aminothiophenol, and a unique solvent effect are presented. The aminothiophenol was deprotected from rearrangement products as well as after derivatization to useful synthons.
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