Visible-Light-Induced Organophotocatalytic Difunctionallization: Open-Air Hydroxysulfurization of Aryl Alkenes with Aryl Thiols

• Published in: Journal of organic chemistry Vol. 87; no. 11; pp. 7378 - 7391
• Main Authors: Hong, Jee Eun, Jung, Yeonghun, Min, Dahye, Jang, Minji, Kim, Soomin, Park, Jiyong, Park, Yohan
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 03.06.2022; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; DIFUNCTIONALIZATION; STYRENES; BETA-HYDROXYSULFIDES; ONE-POT SYNTHESIS; SULFUR; DIMETHYL-SULFOXIDE; ENE CLICK REACTION; DEHYDROGENATIVE COUPLING REACTION; DERIVATIVES; PHOTOREDOX CATALYSIS
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.2c00595

Herein, we report a regioselective visible-light-induced organophotoredox catalytic difunctionalization method to prepare β-hydroxysulfides using aryl alkenes and aryl thiols as substrates. The reaction provides a wide substrate scope of aryl alkenes (from simple styrene to complex bioactive compounds) and aryl thiols (from diverse heteroaromatic thiols to nonhetero­aromatic thiols) (total 45 examples, up to 88% yield). Based on the combined experimental and computational studies, we demonstrate that in situ generated hydroperoxyl radicals from O2 in air react with benzylic radicals, which restrains the reaction between benzylic radicals and the acidic form of thiols in a classical thiol–ene radical reaction. We show that difunctionalization is possible due to the choice of bases, diluted substrate concentrations, increment in catalyst loading, and selection of suitable aryl thiols under aerobic conditions. Considering the biological importance of heteroaromatic thiols and the lack of methods to install them, our approach offers a platform to derive various β-hydroxysulfides that contain aromatic elements.