Thianthrenium-enabled sulfonylation via electron donor-acceptor complex photoactivation

Granados, Albert; Cabrera-Afonso, María Jesús; Escolano, Marcos; Badir, Shorouk O.; Molander, Gary A.

doi:10.1016/j.checat.2022.03.007

Cited by 65 publications

(40 citation statements)

References 48 publications

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“…Sulfones are centrally important synthetic intermediates, pharmacophores, and functional linchpins in materials science applications (Scheme A) . Their notable metabolic and physicochemical stability, as well as a distinctive chemical reactivity imparted by the sulfonyl group, have resulted in a growing number of applications that require facile and rapid synthetic access to structurally diverse sulfone-containing molecules . Given the structural and electronic similarity between the sulfonyl and the carbonyl groups, sulfones have emerged as efficient bioisosteric replacements for reactive carboxylic acids and other carbonyls .…”

Section: Introductionmentioning

confidence: 99%

Tricomponent Decarboxysulfonylative Cross-coupling Facilitates Direct Construction of Aryl Sulfones and Reveals a Mechanistic Dualism in the Acridine/Copper Photocatalytic System

et al. 2022

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Dual catalytic systems involving photocatalytic activation and transition metal-catalyzed steps have enabled innovative approaches to the construction of carbon–carbon and carbon–heteroatom bonds. However, the mechanistic complexity of the dual catalytic processes presents multiple challenges for understanding of the roles of divergent catalytic species that can impede the development of future synthetic methods. Here, we report a dual catalytic process that enables the previously inaccessible, broad-scope, direct conversion of carboxylic acids to aromatic sulfonescentrally important carbonyl group bioisosteric replacements and synthetic intermediatesby a tricomponent decarboxysulfonylative cross-coupling with aryl halides. Detailed mechanistic and computational studies revealed the roles of the copper catalysts, bases, and halide anions in channeling the acridine/copper system via a distinct dual catalytic manifold. In contrast to the halide-free decarboxylative conjugate addition that involves cooperative dual catalysis via low-valent copper species, the halide counteranions divert the decarboxysulfonylative cross-coupling with aryl halides through a two-phase, orthogonal relay catalytic manifold, comprising a kinetically coupled (via antithetical inhibitory and activating roles of the base in the two catalytic cycles), mechanistically discrete sequence of a photoinduced, acridine-catalyzed decarboxylative process and a thermal copper-catalyzed arylative coupling. The study underscores the importance of non-innocent roles of counteranions and key redox steps at the interface of catalytic cycles for enabling previously inaccessible dual catalytic transformations.

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Section: Introductionmentioning

confidence: 99%

Tricomponent Decarboxysulfonylative Cross-coupling Facilitates Direct Construction of Aryl Sulfones and Reveals a Mechanistic Dualism in the Acridine/Copper Photocatalytic System

et al. 2022

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“…[14] Recently, Ritter and others developed the ipsofunctionalization of aryl and alkenyl thianthrenium salts via metal-catalyzed cross-coupling and radical reactions (Scheme 1b, top). [15][16][17][18][19] In 2021, Wickens and our group independently reported the functionalization of alkenes by thianthrenation to formally transform allylic CÀ H bond to form CÀ C, CÀ O, and CÀ N bonds with C-, O-, and N-based nucleophiles (Scheme 1b, bottom). [20] In 2021, Wickens reported electrochemical aziridination of terminal aliphatic alkenes with aliphatic primary amines by thianthrenation (Scheme 1c).…”

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confidence: 99%

Intermolecular Metal‐Free Cyclopropanation and Aziridination of Alkenes with XH₂(X=N, C) by Thianthrenation**

Liu

Cui

et al. 2022

Angew Chem Int Ed

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Three-membered cyclic structures are widely existing in natural products and serve as enabling intermediates in organic synthesis. However, the efficient and straightforward access to such structures with diversity remains a formidable challenge. Herein, a general and practical protocol to aziridines and cyclopropanes synthesis using free XH 2 (X = C or N) with alkenes by thianthrenation is presented. This metal-free protocol features the direct aziridination and cyclopropanation with unprotected XH 2 . Free sulfonamides, amides, carbamates, amines, and methylene with acidic protons, are good precursors, providing an attractive alternative for straightforward synthesis of aziridines and cyclopropanes from easily available starting materials.

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“…to the feasible accessibility of aryl sulfonium salts from simple arenes via regioselective electrophilic thianthrenation or phenoxathiination (Figure 1b) [22][23][24] . In comparison with aryl halides and their analogues, the corresponding arylthianthrenium salts present unique reactivities in both transition metal catalyzed cross-coupling reactions as an aryl electrophile 23,[25][26][27][28][29][30][31][32] and photoredox catalyzed radical coupling reactions as an aryl radical precursor 24,[34][35][36][37][38][39][40] . Most importantly, several novel reaction processes with arylthianthrenium salts, including Pd-catalyzed tritiation 32 , photocatalyzed radical coupling, 24,[34][35][36][37][38][39][40] and electron donor-acceptor complex photoactivation 39,40 etc., have been proven to be inert or inefficient with aryl halides and their analogues.…”

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confidence: 99%

“…In comparison with aryl halides and their analogues, the corresponding arylthianthrenium salts present unique reactivities in both transition metal catalyzed cross-coupling reactions as an aryl electrophile 23,[25][26][27][28][29][30][31][32] and photoredox catalyzed radical coupling reactions as an aryl radical precursor 24,[34][35][36][37][38][39][40] . Most importantly, several novel reaction processes with arylthianthrenium salts, including Pd-catalyzed tritiation 32 , photocatalyzed radical coupling, 24,[34][35][36][37][38][39][40] and electron donor-acceptor complex photoactivation 39,40 etc., have been proven to be inert or inefficient with aryl halides and their analogues. Accordingly, the direct functionalization of arenes via corresponding arylthianthrenium salts has become an appealing approach for the late-stage modification of drug molecules and bioactive molecules.…”

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confidence: 99%

Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons

Chen

Bai

et al. 2022

Preprint

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Great success in synthetic chemistry is motivated by the development of novel and reactive linchpins for carbon-carbon and carbon-heteroatom bond formation reactions, that has dramatically altered chemists’ approach to building molecules. Herein, we report the readily synthesis of aryl sulfonium salts, a novel versatile electrophilic linchpin, via an unprecedented Cu-mediated thianthrenation and phenoxathiination of commercially available arylborons with thianthrene and phenoxathiine, providing a series of aryl sulfonium salts in high efficiency. More importantly, by leveraging the sequential Ir-catalyzed C–H borylation and Cu-mediated thianthrenation of arylborons, the formal thianthrenation of arenes are also achieved. As the Ir-catalyzed C–H borylation with undirected arenes normally occurred at the less steric hindrance position, thus providing a complementary method for thianthrenation of arenes in comparison with the electrophilic thianthrenation. This process is capable of late-stage functionalization of a series of pharmaceuticals, which might find wide synthetic applications in both industry and academic sectors.

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Thianthrenium-enabled sulfonylation via electron donor-acceptor complex photoactivation

Cited by 65 publications

References 48 publications

Tricomponent Decarboxysulfonylative Cross-coupling Facilitates Direct Construction of Aryl Sulfones and Reveals a Mechanistic Dualism in the Acridine/Copper Photocatalytic System

Tricomponent Decarboxysulfonylative Cross-coupling Facilitates Direct Construction of Aryl Sulfones and Reveals a Mechanistic Dualism in the Acridine/Copper Photocatalytic System

Intermolecular Metal‐Free Cyclopropanation and Aziridination of Alkenes with XH₂(X=N, C) by Thianthrenation**

Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons

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Thianthrenium-enabled sulfonylation via electron donor-acceptor complex photoactivation

Cited by 65 publications

References 48 publications

Tricomponent Decarboxysulfonylative Cross-coupling Facilitates Direct Construction of Aryl Sulfones and Reveals a Mechanistic Dualism in the Acridine/Copper Photocatalytic System

Tricomponent Decarboxysulfonylative Cross-coupling Facilitates Direct Construction of Aryl Sulfones and Reveals a Mechanistic Dualism in the Acridine/Copper Photocatalytic System

Intermolecular Metal‐Free Cyclopropanation and Aziridination of Alkenes with XH2(X=N, C) by Thianthrenation**

Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons

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Intermolecular Metal‐Free Cyclopropanation and Aziridination of Alkenes with XH₂(X=N, C) by Thianthrenation**