TEMPO-mediated late stage photochemical hydroxylation of biaryl sulfonium salts

Zhao, Yue; Yu, Congjun; Liang, Wenjing; Atodiresei, Iuliana; Patureau, Frédéric W.

doi:10.1039/d1cc07057f

Cited by 13 publications

(10 citation statements)

References 42 publications

(45 reference statements)

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“…Supporting this hypothesis, the corresponding TEMPO adduct 5 was detected by GC-MS analysis of the crude reaction mixture ( m / z = 309.2, see SI). This result is in good agreement with the literature, in particular with a previous study from our group, wherein TEMPO could be coupled to aryl sulfonium salts in a radical fashion in order to furnish the corresponding phenols, albeit in very different (catalyst-free) conditions …”

supporting

confidence: 92%

“…Furthermore, Stern–Volmer experiments feature significantly stronger fluorescence quenching of the Ru(II) photocatalyst with TMEDA, − as with 2a or 3a , respectively (see SI for details). Combining the above mechanistic insights as well as previous reports, ,,− ,− we then explored the reaction pathway with DFT calculations (Scheme , see SI for details). The photoexcited Ru(II)* species should undergo reductive quenching with TMEDA through single electron transfer (SET, Δ G = 6.8 kcal mol –1 ), furnishing a reduced Ru(I) species (step I ), which would in turn undergo another SET with sulfonium salt 2 (step II ) and regenerate the photocatalyst.…”

mentioning

confidence: 93%

“…The late stage C–H thianthrenation route was notably developed by Ritter and coauthors for this purpose (Scheme , eq 2). Procter and coauthors likewise investigated the coupling of some sulfonium salt building blocks, utilizing a phenothiazine derivative as the photocatalyst. − …”

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confidence: 99%

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Gem-Difluoroallylation of Aryl Sulfonium Salts

et al. 2022

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The unprecedented photochemical late-stage defluorinative gem-difluoroallylation of aryl sulfonium salts, which are formed site-selectively by direct C(sp 2 )�H functionalization, is herein disclosed. This method is distinguished by its mild reaction conditions, wide scope, and excellent site-selectivity. As showcase examples, a Flurbiprofen and Pyriproxyfen derivatives could be late stage C(sp 2 )�H gem-difluoroallylated with high yields. Experimental and computational investigations were conducted.

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Gem-Difluoroallylation of Aryl Sulfonium Salts

et al. 2022

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“…In 2022, the Patureau group explored the reactivity of aryl sulfonium salts (231) in the photochemical hydroxylation reactions with the utilization of 4-Oxo-TEMPO (233) as a promoter and the oxygen source under UV light irradiation (254 nm) (Scheme 48a). [134] The substrate scope and limitation were intensively investigated, indicating that various functional groups (such as ester, carbonyl, halogen, cyano and imidazole etc.) were well tolerated to deliver the corresponding products 232 in good to excellent yields.…”

Section: C(sp 2 ) à Oh Bond Formationmentioning

confidence: 99%

Recent Advances in Carbon‐Nitrogen/Carbon‐Oxygen Bond Formation Under Transition‐Metal‐Free Conditions

Zhang

Song

Shi

et al. 2023

The Chemical Record

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Carbon‐heteroatom bond formation under transition‐metal free conditions provides a powerful synthetic alternative for the efficient synthesis of valuable molecules. In particular, C−N and C−O bonds are two important types of carbon‐heteroatom bonds. Thus, continuous efforts have been deployed to develop novel C−N/C−O bond formation methodologies involving various catalysts or promoters under TM‐free conditions, which enables the synthesis of various functional molecules comprising C−N/C−O bonds in a facile and sustainable manner. Considering the significance of C−N/C−O bond construction in organic synthesis and materials science, this review aims to comprehensively present selected examples on the construction of C−N (including amination and amidation) and C−O (including etherification and hydroxylation) bonds without transition metals. Besides, the involved promoters/catalysts, substrate scope, potential application and possible reaction mechanisms are also systematically discussed.

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“…In 2022, the Patureau group utilized a similar strategy to produce arylated phenols under metal-free conditions using TEMPO as the oxygen source. 32…”

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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TEMPO-mediated late stage photochemical hydroxylation of biaryl sulfonium salts

Abstract: The late stage photochemical hydroxylation of biaryl sulfonium salts was enabled with a TEMPO derivative as a simple oxygen source, in metal free conditions.

Cited by 13 publications

References 42 publications

Gem-Difluoroallylation of Aryl Sulfonium Salts

Gem-Difluoroallylation of Aryl Sulfonium Salts

Recent Advances in Carbon‐Nitrogen/Carbon‐Oxygen Bond Formation Under Transition‐Metal‐Free Conditions

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

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