Divergent Functionalization of Styrenes via Radical/Polar Crossover with CO2 and Sodium Sulfinates

• Published in: Chemistry : a European journal 2023-04, Vol.29 (19), p.e202203625-n/a
• Main Authors: Benedetti Vega, Kimberly, Campos Delgado, José Antonio, Pugnal, Lucas V. B. L., König, Burkhard, Menezes Correia, José Tiago, Weber Paixão, Márcio
• Format: Article
• Language: English
• Subjects: Acrylates; Agrochemicals; Carbon dioxide; Carboxylic acids; Chemistry; Coupling (molecular); Functional groups; photocatalysis; Sodium; Styrenes; Sulfones; sustainability; α-substituted acrylates
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202203625

Sulfones and carboxylic acids are prominent motifs widely present in the chemical structure of agrochemicals, pharmaceuticals and many other highly valuable compounds. Herein, we describe a conjunctive strategy for the precise installation of these functionalities onto styrenes using sodium sulfinates and CO2 as coupling partners. The protocol allowed the preparation of carboxy‐sulfonylated compounds in good yields and broad functional group tolerance. Additionally, taking advantage of the leaving group ability of the sulfone moiety, a one‐pot photocatalytic carboxy‐sulfonylation‐elimination strategy was developed for the synthesis of α‐aryl‐acrylates. Not so radical: The amalgamation of radical chemistry with polar chemistry is used to develop a tunable multicomponent reaction which involves CO2, sodium sulfinates and styrenes to access both β‐sulfonylateds carboxylic acids through radical–polar crossover process and to α‐substituted acrylates through sequential sulfonyl radical addition/coupling/elimination process. This setup exhibits excellent tolerance to different functional groups and its application towards biologically relevant molecules and product diversification contributes to the synthetic utility of this method.