B(C6F5)3 Catalyzed regiodivergent thioetherifications of alkenes via thiiranium intermediates: experimental and computational insights

Alotaibi, Nusaybah, Babaahmadi, Rasool, Das, Sampurna, Richards, Emma ORCID: https://orcid.org/0000-0001-6691-2377, Wirth, Thomas ORCID: https://orcid.org/0000-0002-8990-0667, Pramanik, Milan and Melen, Rebecca ORCID: https://orcid.org/0000-0003-3142-2831 2024. B(C6F5)3 Catalyzed regiodivergent thioetherifications of alkenes via thiiranium intermediates: experimental and computational insights. Chemistry - A European Journal , e202404236. 10.1002/chem.202404236

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Abstract

Precise control of selective alkene functionalization is a continuing challenge in the chemical community. In this study, we develop a substitution‐controlled regiodivergent thioetherification of di‐ or trisubstituted alkenes using 10 mol% tris(pentafluorophenyl)borane [B(C6F5)3] as a catalyst and N–thiosuccinimide as a sulfenylating reagent. This metal‐free borane catalyzed C–S bond forming method is utilized for a Csp2–H sulfenylation reaction to synthesize an array of diphenylvinylsulfide derivatives with good to excellent yields (25 examples, up to 91% yield). Some of the products exhibit aggregation‐induced emission luminogen properties used in organic light–emitting diodes (OLEDs), chemical sensors, and biological imaging units. Depending upon the starting alkene, Csp3–S sulfenylation products could also be generated regioselectively. A variety of allylic thioethers from α‐alkyl substituted styrenes were isolable in good yields and selectivities (14 examples, up to 67% yield). The DFT‐supported mechanistic study confirms that the reaction proceeds via a thiiranium ion intermediate, where the regioselectivity and product formation are determined by the alkene substituents which influences the activation barriers and energy profiles. Diphenylvinylsulfide derivatives can also be efficiently transformed into a range of synthetically valuable compounds, including vinyl sulfoxides, vinyl sulfones, and vinyl sulfoximines.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Chemistry
Additional Information:	License information from Publisher: LICENSE 1: URL: http://onlinelibrary.wiley.com/termsAndConditions#vor, Start Date: 2024-12-09
Publisher:	Wiley
ISSN:	0947-6539
Date of First Compliant Deposit:	18 December 2024
Date of Acceptance:	9 December 2024
Last Modified:	06 Jan 2025 10:24
URI:	https://orca.cardiff.ac.uk/id/eprint/174807

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