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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Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds

Chemical Communications, Год журнала: 2023, Номер 59(36), С. 5343 - 5364

Опубликована: Янв. 1, 2023

The activation and transformation of organic chemical bonds is a fundamental scientific problem. In the past several decades, C-S bond cleavage for construction C-C C-heteroatom has received tremendous attention in chemistry. Although significant progress been made field transition metal strategies, variety novel transition-metal-free strategies have also developed using halogenated reagents, oxidants, acids, bases. Moreover, photochemical electrochemical methods to achieve organosulfur compounds. To date, however, no comprehensive review reported. Therefore, we herein provide major advances compounds, including thioethers, sulfoxides, sulfones, thioacetals, sulfonium salts, sulfur ylides.

Язык: Английский

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Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 15, 2024

Abstract Direct and site-selective C-H functionalization of alkenes under environmentally benign conditions represents a useful attractive yet challenging transformation to access value-added molecules. Herein, unified protocol for variety intermolecular Heck-type functionalizations C sp2 -H bond has been developed by thianthrenation. The reaction features metal-free operationally simple exclusive cine -selective aliphatic aryl forge C-C, C-N, C-P, C-S bonds at room temperature, providing general with nucleophiles (Nu = sulfinates, cyanides, amines, amides). Alkenes undergo -sulfonylation, cyanation, amination afford alkenyl sulfones, nitriles enamines.

Язык: Английский

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Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(51), С. 21503 - 21510

Опубликована: Дек. 16, 2021

Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strategies remain limited with respect the viable N-substituents. Herein, we disclose a new electrochemical process prepare aliphatic by coupling two abundant starting materials: secondary and unactivated alkenes. This oxidative transformation proceeds via generation of an electrophilic adduct between thianthrene alkene substrates. Treatment these adducts nucleophiles base provides products in high yield. strategy is also amenable functionalization feedstock gaseous alkenes at 1 atm. In case 1-butene, Z-selective crotylation observed. strategy, however, not synthesis simple building blocks; complex molecules suitable as both partners. Preliminary mechanistic studies implicate vinylthianthrenium salts key reactive intermediates.

Язык: Английский

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Metal-free allylic C–H nitrogenation, oxygenation, and carbonation of alkenes by thianthrenation

Chemical Science, Год журнала: 2021, Номер 13(4), С. 1003 - 1008

Опубликована: Дек. 20, 2021

Selective functionalization of allylic C-H bonds into other chemical is among the most straightforward and attractive, yet challenging transformations. Herein, a transition-metal-free protocol for direct nitrogenation, oxygenation, carbonation alkenes by thianthrenation was developed. This operationally simple allows unified amination, esterification, etherification, arylation vinyl thianthrenium salts. Notably, reaction furnishes multialkyl substituted amines, ammonium salts, sulfonyl amides, esters, ethers in good yields. The proceeds under mild conditions with excellent functional group tolerance could be applied to late-stage allylation natural products, drug molecules peptides chemoselectivity.

Язык: Английский

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Bifunctional sulfilimines enable synthesis of multiple N-heterocycles from alkenes

Nature Chemistry, Год журнала: 2022, Номер 14(8), С. 898 - 904

Опубликована: Июль 25, 2022

Abstract Intramolecular cyclization of nitrogen-containing molecules onto pendant alkenes is an efficient strategy for the construction N-heterocycles, which are paramount importance in, example, pharmaceuticals and materials. Similar intermolecular reactions, however, scarcer nitrogen building blocks, including N-centred radicals, divergent modular versions not established. Here we report use sulfilimines as bifunctional N-radical precursors reactions with to produce N-unprotected heterocycles in a single step through photoredox catalysis. Structurally diverse can be synthesized step, subsequently engage afford synthetically valuable five-, six- seven-membered heterocycles. The broad scope achievable by radical-polar crossover annulation enabled character reagents, distinguishes itself from all other N-centred-radical-based reactions. synthesis allows larger structural diversity N-heterocycle products than currently methods.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(41)

Опубликована: Авг. 17, 2022

Three-membered cyclic structures are widely existing in natural products and serve as enabling intermediates organic synthesis. However, the efficient straightforward access to such with diversity remains a formidable challenge. Herein, general practical protocol aziridines cyclopropanes synthesis using free XH2 (X=C or N) alkenes by thianthrenation is presented. This metal-free features direct aziridination cyclopropanation unprotected . Free sulfonamides, amides, carbamates, amines, methylene acidic protons, good precursors, providing an attractive alternative for of from easily available starting materials.

Язык: Английский

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Sulfonium and Selenonium Salts as Noncovalent Organocatalysts for the Multicomponent Groebke–Blackburn–Bienaymé Reaction

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(15), С. 10199 - 10207

Опубликована: Июль 20, 2022

Sulfonium and selenonium salts, represented by S-aryl dibenzothiophenium Se-aryl dibenzoselenophenium triflates, were found to exhibit remarkable catalytic activity in the model Groebke–Blackburn–Bienaymé reaction. Kinetic analysis density functional theory (DFT) calculations indicated that their effect is induced ligation of reaction substrates σ-holes on S or Se atom cations. The experimental data although 10-fold excess chloride totally inhibits sulfonium salt remains catalytically active, which can be explained experimentally lower binding constant derivative comparison with analogue. Both types salts than dibenziodolium species.

Язык: Английский

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Polarity Transduction Enables the Formal Electronically Mismatched Radical Addition to Alkenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(5), С. 2773 - 2778

Опубликована: Янв. 31, 2023

The formation of carbon-carbon bonds via the intermolecular addition alkyl radicals to alkenes is a cornerstone organic chemistry and plays central role in synthesis. However, unless specific electrophilic are involved, polarity matching requirements restrict alkene component be electron deficient. This limits scope fundamentally important bond forming process that could otherwise more universally applied. Herein, we introduce

Язык: Английский

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Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8299 - 8307

Опубликована: Апрель 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Язык: Английский

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