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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Synthetic Applications of Sulfonium Salts

European Journal of Inorganic Chemistry, Journal Year: 2020, Volume and Issue: 2020(26), P. 2486 - 2500

Published: April 30, 2020

This minireview aims to cover the developments over past two decades in chemistry of sulfonium salts. Specifically, insight is provided into synthetic strategies available for preparation these compounds, different reactivity patterns that are expected depending on their structural features or reaction conditions applied, and diversity organic scaffolds can thereby be synthesized. Additionally, pros cons derived from use salts presented critically compared, when possible, relation reagents not based sulfur but depicting similar reactivity.

Language: Английский

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Radical C−C Bond Formation using Sulfonium Salts and Light

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(11), P. 2135 - 2142

Published: March 3, 2020

Abstract Sulfonium salts are playing an increasingly significant role in contemporary organic synthesis. In particular, the generation of radicals from sulfonium is a fundamental process Nature and has been subject investigation for over 50 years. However, general synthetic methods that use as radical precursors rare. The advent photoredox catalysis triggered upsurge interest chemistry this review surveys recent applications aryl‐ alkylsulfonium light‐mediated, C−C bond formation. magnified image

Language: Английский

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The Interrupted Pummerer Reaction: Design of Sulfoxides and Their Utility in Organic Synthesis

Heterocycles, Journal Year: 2021, Volume and Issue: 102(5), P. 783 - 783

Published: Jan. 1, 2021

Acid anhydride-activated sulfoxides can undergo a variety of cascade reactions after reacting with nucleophiles on its sulfur atom.Originally regarded as an abnormal phenomenon that occurs under Pummerer reaction conditions, the reports increased gradually, and research regarding sulfoxide reactivity has advanced.In recent years, term 'interrupted reaction' been introduced, transformation actively incorporated into development new areas.Such studies have yielded numerous valuable sulfoxides, which contribute to precise control generation practical products.Notably, outcome interrupted is characteristic for each nucleophile.CONTENTS 1. Introduction 2. Reactions alcohols 3. phenols 4. amines, amides, nitriles 5. enolizable ketones 6.Reactions alkenes alkynes 7. arenes heteroarenes

Language: Английский

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Catalytic Transformations of Sulfonium Salts via C‐S Bond Activation

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 3356 - 3369

Published: Jan. 7, 2021

Abstract After the 20‐year dormant period since Liebeskind's seminal report, triorganosulfonium salts have now proved to be reliably useful surrogates of or complement organic halides in a variety transition‐metal‐catalyzed transformations. By necessity, my group developed Suzuki‐Miyaura ring‐opening arylation sulfonium dibenzothiophenes with tetraarylborates and Pd‐catalyzed intramolecular C−H/C−S coupling. Following this starting point experiencing decent reactivity salts, order maximize synthetic utility organosulfur compounds, we successfully applied readily available Ni‐catalyzed coupling arylzinc reagents, Pd‐ photoredox‐catalyzed Mizoroki‐Heck reaction, alkoxycarbonylation, Miyaura borylation, reductive carboxylation, zincation. I sincerely hope Personal Account will facilitate further development reactions which are difficult achieve using conventional (pseudo)halides.

Language: Английский

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Alkynyl Sulfonium Salts Can Be Employed as Chalcogen‐Bonding Catalysts and Generate Alkynyl Radicals under Blue‐Light Irradiation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(16)

Published: Feb. 4, 2022

Chalcogen bonding (ChB) has emerged as a promising tool in organic synthesis. However, compared with the well-developed selenium- and tellurium-based salt catalysts, ChB catalysis of sulfonium salts is still unknown. Here, we report new type alkynyl-sulfonium for various ionic transformations, including transfer hydrogenation, bromination, bromolactonization, dimerization 1,1-diphenylethylene, nitro-Michael addition reaction Ritter reaction. More importantly, photocapability was first demonstrated to generate alkynyl radicals synthesis variety chalcogenoacetylenes. Mechanistic studies shed light on mechanism photoinduced reactions confirmed involvement which are difficult otherwise.

Language: Английский

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Asymmetric systematic synthesis, structures, and (chir)optical properties of a series of dihetero[8]helicenes

Chemical Science, Journal Year: 2021, Volume and Issue: 12(8), P. 2784 - 2793

Published: Jan. 1, 2021

A series of dihetero[8]helicenes have been systematically synthesized in enantiomerically enriched forms by utilizing the characteristic transformations organosulfur functionality. The synthetic route begins with assembling a ternaphthyl common intermediate from 2-naphthol and bissulfinylnaphthalene through an extended Pummerer reaction followed facile multi-gram-scale resolution. subsequent cyclization reactions into dioxa- dithia[8]helicenes take place excellent axial-to-helical chirality conversion. Dithia[8]helicene is further transformed nitrogen carbon analogs replacing two endocyclic sulfur atoms via SNAr-based skeletal reconstruction. efficient systematic synthesis has enabled comprehensive evaluation physical properties, which clarified effect on their structures (chir)optical properties as well unexpected conformational stability helical framework.

Language: Английский

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Trifluoromethyl Sulfoxides: Reagents for Metal‐Free C−H Trifluoromethylthiolation

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(37), P. 15918 - 15922

Published: May 28, 2020

Trifluoromethyl sulfoxides are a new class of trifluoromethylthiolating reagent. The engage in metal-free C-H trifluoromethylthiolation with range (hetero)arenes. method is also applicable to the functionalization important compound classes, such as ligand derivatives and polyaromatics, late-stage medicines agrochemicals. isolation characterization sulfonium salt intermediate supports an interrupted Pummerer reaction mechanism.

Language: Английский

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Selective [5,5]‐Sigmatropic Rearrangement by Assembly of Aryl Sulfoxides with Allyl Nitriles

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(16), P. 5316 - 5320

Published: Feb. 27, 2019

Abstract Aromatic [5,5]‐sigmatropic rearrangement is an appealing protocol for accessing 1,4‐substituted arenes. However, such a has not been well utilized in organic synthesis because of the difficulties substrates, selectivity issues, and limited substrate scope. Described herein new reaction utilizing readily available aryl sulfoxides allyl nitriles. This features mild conditions, high chemo‐ regioselectivity, excellent functional‐group compatibility, broad Computational studies suggest that success can be attributed to selective electrophilic assembly precursors, which linear ‐C=C=N‐ linkage favors over competitive [3,3]‐sigmatropic rearrangement.

Language: Английский

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Sulfur(IV) in Transition-Metal-Free Cross-Couplings for Biaryl Synthesis

ACS Sustainable Chemistry & Engineering, Journal Year: 2022, Volume and Issue: 10(8), P. 2569 - 2586

Published: Feb. 16, 2022

The reactivity of sulfur(IV) compounds is great current interest among organic chemists. In this Perspective, we discuss the chemistry (namely, sulfoxides, sulfonium salts, and sulfinates) within area transition-metal-free cross-couplings for biaryl synthesis. These sulfur(IV)-based methods show potential in sustainable formation can deliver unique structures that are difficult to access by other means. This Perspective also highlights how versatile has helped design new reagents, mediators, catalysts.

Language: Английский

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