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Updated: May 12, 2026

Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in Poly(S-Divinylbenzene)
Published on: May 20, 2019
Sulfur participation in [3,3]-sigmatropic rearrangements
Roberto Fernández de la Pradilla1, Mariola Tortosa, Alma Viso
1Instituto de Química Orgánica General, Consejo Superior de Investigaciones Científicas, c/ Juan de la Cierva 3, 28006, Madrid, Spain, iqofp19@iqog.csic.es.
Abstract:
The thio-Claisen rearrangement is a general and facile process that is often advantageous overthe standard Claisen rearrangement. Several asymmetric variants of the thio-Claisen rearrangement havebeen reported. The rearrangement of sulfonium salts and sulfoxides takes place even more readily. Alkenylsulfoxides and sulfilimines undergo a highly stereocontrolled cyclization to lactones and lactams,respectively, upon reaction with haloketenes; this synthetically useful process entails a [3,3]-sigmatropicrearrangement of a zwitterionic intermediate. Sulfur-containing functionalities located at the peripheryof the Claisen substrates exert a powerful influence on the outcome of the process.
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