<i>Cine</i>-Substitutions at Five-Membered Hetarenes Enabled by Sulfonium Salts

Berger, Florian; Alvarez, Eva Maria; Frank, Nils; Bohdan, Kostiantyn; Kondratiuk, Mykhailo; Torkowski, Luca; Engl, Pascal S.; Barletta, Joana; Ritter, Tobias

doi:10.1021/acs.orglett.0c02067

Cited by 34 publications

(26 citation statements)

References 34 publications

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“…In 2020, the Ritter group reported a cine -substitution of electron-rich heteroarylsulfonium salts where various N -containing heterocycles were used as N -nucleophiles. 30 This cine -substitution goes through a novel reaction pathway elucidated in Scheme 22 , that is, the sulfur ylide is formed after addition of the nucleophile to the heteroarylsulfonium salt, followed by the protonation and elimination to give the final product. It should be noted that in this chemistry, the sulfonium group showed distinguished leaving ability from other (pseudo)halides.…”

Section: Thianthrenation-enabled Site-selective Functionalization Of ...mentioning

confidence: 99%

Recent Advances in Thianthrenation/Phenoxathiination Enabled Site-Selective Functionalization of Arenes

Wang

Chen

2022

Synthesis

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Site-selective functionalization of simple arenes remains a paramount challenge due to the similarity of multiple C–H bonds in the same molecule with similar steric environment and electronic properties. Recently, the site-selective thianthrenation/phenoxathiination of arenes has become an attractive solution to reach this challenging goal and it has been applied in the late-stage functionalization of various bioactive molecules. This short review aims to summarize recent advances in the site-selective C–H functionalization of arenes via aryl thianthrenium salts, as well as mechanistic insights in the remarkable site-selectivity obtained in thianthrenation step.1 Introduction2 Site-Selective Thianthrenation of Arenes and Mechanistic Insight3 Thianthrenation-Enabled Site-Selective Functionalization of Arenes3.1 Thianthrenation-Enabled C(sp 2)–C Bond Formation Reaction3.2 Thianthrenation-Enabled C(sp 2)–X Bond Formation Reaction4 Conclusion and Outlook

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Section: Thianthrenation-enabled Site-selective Functionalization Of ...mentioning

confidence: 99%

Recent Advances in Thianthrenation/Phenoxathiination Enabled Site-Selective Functionalization of Arenes

Wang

Chen

2022

Synthesis

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“…The combination of cine substitution with site-selective C-H functionalization allows the synthesis of arenes with unusual substitution patterns, which are hard to access otherwise (Scheme 11). 22 Scheme 11 Cine substitution of heterocyclic sulfonium salts 22…”

Section: Cine Substitutionmentioning

confidence: 99%

Site-Selective Late-Stage C–H Functionalization via Thianthrenium Salts

Berger¹,

Ritter²

2021

Synlett

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The high abundance of C–H bonds in organic molecules makes C–H functionalization a powerful approach to quickly increase the complexity of an organic molecule. However, the high abundance of C–H bonds also provides a challenge to C–H functionalization reactions: selectivity. While most C–H functionalization reactions produce mixtures of different products for most substrates, we have developed a highly selective method for aromatic C–H functionalization via sulfonium salts. The reaction does not require a certain directing group to be selective. The introduced functional group is a sulfonium group, which participates in various follow-up reactions such as palladium-catalyzed cross-coupling reactions and photoredox catalysis. Here we discuss our pathway to develop the reaction as well as its scope and utility.1 Introduction2 Site-Selective Synthesis of Sulfonium Salts3 Sulfonium Salts in Palladium-Catalyzed Cross-Coupling4 Sulfonium Salts in Photoredox Catalysis5 Sulfur(IV) Reductive Elimination6 Cine Substitution7 Conclusion

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“…Recently, sulfonium salts have been attracting increasing attention due to their broad applications in carbon-carbon and carbon-heteroatom bond formation reactions, [22][23][24][25][26][27][28][29][30][31][32][33][34] especially for the construction of C-N bonds. In 2019, the Ritter group reported the first C(sp 2 )-N cross-coupling reaction of aryl thianthrenium salts (Scheme 1a, top).…”

Section: Introductionmentioning

confidence: 99%