Decarboxylative Sulfinylation Enables a Direct, Metal-Free Access to Sulfoxides from Carboxylic Acids.

Autor: Nguyen VD; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA., Haug GC; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA., Greco SG; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA., Trevino R; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA., Karki GB; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA., Arman HD; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA., Larionov OV; Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Oct 24; Vol. 61 (43), pp. e202210525. Date of Electronic Publication: 2022 Sep 09.
DOI: 10.1002/anie.202210525
Abstrakt: The intermediate oxidation state of sulfoxides is central to the plethora of their applications in chemistry and medicine, yet it presents challenges for an efficient synthetic access, limiting the structural diversity of currently available sulfoxides. Here, we report a data-guided development of direct decarboxylative sulfinylation that enables the previously inaccessible functional group interconversion of carboxylic acids to sulfoxides in a reaction with sulfinates. Given the broad availability of carboxylic acids and the growing synthetic potential of sulfinates, the direct decarboxylative sulfinylation is poised to improve the structural diversity of synthetically accessible sulfoxides. The reaction is facilitated by a kinetically favored sulfoxide formation from the intermediate sulfinyl sulfones, despite the strong thermodynamic preference for the sulfone formation, unveiling the previously unknown and chemoselective radicalophilic sulfinyl sulfone reactivity.
(© 2022 Wiley-VCH GmbH.)
Databáze: MEDLINE
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