Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(14), P. 8701 - 8780

Published: June 25, 2019

Organosulfur compounds have long played a vital role in organic chemistry and the development of novel chemical structures architectures. Prominent among these organosulfur are those involving sulfur(IV) center, which been subject countless investigations over more than hundred years. In addition to list textbook sulfur-based reactions, there has sustained interest organosulfur(IV) recent Of particular within is ease with synthetic chemist can effect wide range transformations through either bond formation or cleavage at sulfur. This review aims cover developments past decade molecules provide insight into both reactions critically rely on this versatile element diverse scaffolds that thereby be synthesized.

Language: Английский

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Transition-metal mediated carbon–sulfur bond activation and transformations: an update

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(13), P. 4307 - 4359

Published: Jan. 1, 2020

This review summarizes the advances in transition-metal-catalyzed cross-couplingviacarbon–sulfur bond activation and cleavage since late 2012 as an update of critical published early 2013 (Chem. Soc. Rev., 2013,42, 599–621).

Language: Английский

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Organothianthrenium salts: synthesis and utilization

Chemical Science, Journal Year: 2022, Volume and Issue: 13(46), P. 13690 - 13707

Published: Jan. 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.

Language: Английский

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Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 10431 - 10440

Published: April 26, 2023

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

Language: Английский

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An Interrupted Pummerer/Nickel‐Catalysed Cross‐Coupling Sequence

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(31), P. 9785 - 9789

Published: June 8, 2018

An interrupted Pummerer/nickel-catalysed cross-coupling strategy has been developed and used in the elaboration of styrenes. The operationally simple method can be carried out as a one-pot process, involves direct formation stable alkenyl sulfonium salt intermediates, utilises commercially available sulfoxide, catalyst, ligand, operates at ambient temperature, accommodates sp-, sp2 -, sp3 -hybridised organozinc coupling partners, delivers functionalised styrene products high yields over two steps. Pummerer/cyclisation approach also to access carbo- heterocyclic salts for cross-coupling.

Language: Английский

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Para-selective borylation of monosubstituted benzenes using a transient mediator

Science China Chemistry, Journal Year: 2019, Volume and Issue: 63(3), P. 336 - 340

Published: Nov. 27, 2019

Language: Английский

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A leap forward in sulfonium salt and sulfur ylide chemistry

Chinese Chemical Letters, Journal Year: 2020, Volume and Issue: 32(1), P. 299 - 312

Published: June 3, 2020

Language: Английский

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Recent development of ortho -C–H functionalization of aryl sulfoxides through [3,3] sigmatropic rearrangement

Tetrahedron Letters, Journal Year: 2018, Volume and Issue: 59(31), P. 2951 - 2959

Published: June 26, 2018

Language: Английский

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High Site Selectivity in Electrophilic Aromatic Substitutions: Mechanism of C–H Thianthrenation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(39), P. 16041 - 16054

Published: Sept. 21, 2021

The introduction of thianthrene as a linchpin has proven to be versatile strategy for the C–H functionalization aromatic compounds, featuring broad scope and fast diversification. synthesis aryl thianthrenium salts displayed an unusually high para regioselectivity, notably superior those observed in halogenation or borylation reactions various substrates. We report experimental computational study on mechanism thianthrenation reactions, with emphasis elucidation reactive species nature exquisite site selectivity. Mechanisms involving direct attack arene isolated O-trifluoracetylthianthrene S-oxide (TT+-TFA) dication (TT2+) via electron transfer under acidic conditions are identified. A reversible interconversion different Wheland-type intermediates before subsequent, irreversible deprotonation is proposed responsible exceptional selectivity reaction.

Language: Английский

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Ni-Catalyzed Carboxylation of C(sp²)–S Bonds with CO₂: Evidence for the Multifaceted Role of Zn

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(3), P. 2117 - 2123

Published: Jan. 15, 2020

Nickel-catalyzed reductive carboxylation reactions of aryl electrophiles typically require the use metallic reducing agents. At present, prevailing perception is that these serve as both a source electrons and Lewis acids may aid CO2 insertion into Ni–C bond. Herein, we provide evidence for in situ formation organometallic species from reductant, step has either been ruled out or unexplored catalytic with metal powder reductants. Specifically, demonstrate Zn(0) acts reductant Zn(II) generates arylzinc might play role C(sp2)–S arylsulfonium salts. Overall, Ni-catalyzed reaction proceeds under mild conditions non-amide solvent, displays wide substrate scope, can be applied to formal para C–H arenes.

Language: Английский

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