Organothianthrenium salts: synthesis and utilization

Chemical Science, Год журнала: 2022, Номер 13(46), С. 13690 - 13707

Опубликована: Янв. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Язык: Английский

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Vinyl Thianthrenium Tetrafluoroborate: A Practical and Versatile Vinylating Reagent Made from Ethylene

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 12992 - 12998

Опубликована: Авг. 10, 2021

The use of vinyl electrophiles in synthesis has been hampered by the lack access to a suitable reagent that is practical and appropriate reactivity. In this work we introduce thianthrenium salt as an effective vinylating reagent. bench-stable, crystalline can be readily prepared from ethylene gas at atmospheric pressure one step broadly useful annulation chemistry (hetero)cycles, N-vinylation heterocyclic compounds, palladium-catalyzed cross-coupling reactions. structural features thianthrene core enable distinct reactivity profile, unprecedented for other sulfonium derivatives.

Язык: Английский

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Photoredox-Catalyzed α-Sulfonylation of Ketones from Sulfur Dioxide and Thianthrenium Salts

Organic Letters, Год журнала: 2022, Номер 24(15), С. 2955 - 2960

Опубликована: Апрель 13, 2022

A photoredox-catalyzed sulfonylation of silyl enol ethers with DABCO·(SO2)2 and thianthrenium salts is achieved, providing diverse β-keto sulfones in moderate to good yields. This protocol features easily accessible starting materials functional group compatibility, enabling the introduction various functionalized sulfonyl groups into ketones. Furthermore, as one important industrial raw materials, methanol can be employed methyl source prepare α-methylsulfonated ketones through a intermediate for first time.

Язык: Английский

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

Synthesis, Год журнала: 2022, Номер 54(18), С. 3928 - 3940

Опубликована: Июнь 28, 2022

Abstract Site-selective functionalization of simple arenes remains a paramount challenge due to the similarity multiple C–H bonds in same molecule with similar steric environment and electronic properties. Recently, site-selective thianthrenation/phenoxathiination has become an attractive solution reach this challenging goal it been applied late-stage various bioactive molecules. This short review aims summarize recent advances via aryl thianthrenium salts, as well mechanistic insights remarkable site-selectivity obtained thianthrenation step. 1 Introduction 2 Site-Selective Thianthrenation Arenes Mechanistic Insight 3 Thianthrenation-Enabled Functionalization 3.1 C(sp 2)–C Bond Formation Reaction 3.2 2)–X 4 Conclusion Outlook

Язык: Английский

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Site-selective carbonylation of arenes via C(sp2)-H thianthrenation: Palladium-catalyzed direct access to α,β-unsaturated ketones

Journal of Catalysis, Год журнала: 2024, Номер 432, С. 115454 - 115454

Опубликована: Март 20, 2024

Язык: Английский

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Construction of α-Amino Azines via Thianthrenation-Enabled Photocatalyzed Hydroarylation of Azine-Substituted Enamides with Arenes

Organic Letters, Год журнала: 2021, Номер 23(21), С. 8522 - 8526

Опубликована: Окт. 18, 2021

α-Amino azines are widely found in pharmaceuticals and ligands. Herein, we report a practical method for accessing this class of compounds via photocatalyzed hydroarylation azine-substituted enamides with the situ-generated aryl thianthrenium salts as radical precursor. This reaction features broad substrate scope, good functional group tolerance, mild conditions is suitable late-stage installation α-amino complex structures.

Язык: Английский

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Transition-Metal-Free, Formal C–H Germylation of Arenes and Styrenes via Dibenzothiophenium Salts

Organic Letters, Год журнала: 2021, Номер 23(12), С. 4779 - 4784

Опубликована: Июнь 4, 2021

We report an operationally simple, selective, and transition-metal-free germylation of arenes styrenes at room temperature, using a robust bench-stable Ge source (R3Ge-SiR3) dibenzothiophenium salts as enabling intermediates. The first direct engagement in cross-coupling the newly made E-alkenyl germanes is also presented, allowing chemoselective arylation under air-tolerant nanoparticle catalysis.

Язык: Английский

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Visible-light-initiated catalyst-free trifluoromethylselenolation of arylsulfonium salts with [Me₄N][SeCF₃]

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(8), С. 2220 - 2227

Опубликована: Янв. 1, 2022

Catalyst-free visible-light irradiation has leveraged the big redox potential gaps between arylsulfonium salts and [Me 4 N][SeCF 3 ], which combined with sulfenylation processes offers convenient selective C–H trifluoromethylselenolation.

Язык: Английский

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Torsional strain inversed chemoselectivity in a Pd-catalyzed atroposelective carbonylation reaction of dibenzothiophenium

Chemical Science, Год журнала: 2022, Номер 13(13), С. 3761 - 3765

Опубликована: Янв. 1, 2022

A palladium-catalyzed enantioselective ring-opening/carbonylation of cyclic diarylsulfonium salts is reported. In comparison to thioethers, the sulfonium displayed high reactivity and enabled reaction be performed under mild conditions (room temperature). The steric repulsion two non-hydrogen substituents adjacent axis led distorted, which ring-opening proceed with significant preference for breaking exocyclic C-S bond.

Язык: Английский

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Palladium-Catalyzed Synthesis of Esters from Arenes through C–H Thianthrenation

Organic Letters, Год журнала: 2022, Номер 24(32), С. 6031 - 6036

Опубликована: Авг. 5, 2022

The efficient palladium-catalyzed synthesis of esters from readily available arenes has been developed. These C–H bond esterifications were achieved relying on the regioselective thianthrenation to generate aryl-TT salts, which treated as reactive electrophilic substrates couple with phenol formate and N-hydroxysuccinimide (NHS) giving access NHS esters, respectively, in absence carbon monoxide. A wide range functional could be prepared high efficiency under this redox-neutral palladium-catalytic condition. Late-stage functionalization investigations synthetic applications demonstrated potential application established platform these products.

Язык: Английский

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