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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Blue‐Light‐Induced Carbene‐Transfer Reactions of Diazoalkanes

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(4), P. 1203 - 1207

Published: Nov. 27, 2018

Abstract Carbenes are very important reactive intermediates to access a variety of complex molecules and applied widely in organic synthesis drug discovery. Typically, their chemistry is accessed by the use transition metal catalysts. Herein, we describe application low‐energy blue light for photochemical generation carbenes from donor–acceptor diazoalkanes. This catalyst‐free operationally simple approach enables highly efficient cyclopropenation reactions with alkynes rearrangement sulfides under mild reaction conditions, which can be utilized both batch continuous‐flow processes.

Language: Английский

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Lightening Diazo Compounds?

ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(27), P. 8895 - 8918

Published: June 25, 2021

The development of new sustainable reactions and protocols is essential to fulfill the growing demands every branch organic chemistry for greener synthetic methodologies. In this context, use visible light as only source energy highly appealing. Since diazo compounds are valuable reagents in synthesis, their transformations realized a manner interest. High reactivity easy availability make them suitable solar-driven transformations. Indeed, photochemical have recently proven alternative transition metal catalysis. perspective, we highlight applications these under irradiation, particularly focusing on recent advancements. These include generation carbenes radicals which involve many relevant reactions, [2+1]-cycloadditions, X–H C–H insertions, Wolff rearrangement, more. Mechanistic aspects processes briefly addressed give readers deeper understanding rules underlying photoreactivity compounds. We conclude by emphasizing significant advancements discussing challenges future developments photochemistry reagents.

Language: Английский

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Recent Perspectives on Rearrangement Reactions of Ylides via Carbene Transfer Reactions

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(4), P. 1270 - 1281

Published: Aug. 5, 2020

Abstract Among the available methods to increase molecular complexity, sigmatropic rearrangements occupy a distinct position in organic synthesis. Despite being known for over century rearrangement reactions of ylides via carbene transfer reaction have only recently come age. Most ylide mediated processes involve rupture σ‐bond and formation new bond between π‐bond negatively charged atom followed by simultaneous redistribution π‐electrons. This minireview describes advances this research area made recent years, which now opens up metal‐catalyzed enantioselective reactions, metal‐free photochemical novel pathways that can be accessed intermediates.

Language: Английский

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Sulfur-Based Ylides in Transition-Metal-Catalysed Processes

Topics in Current Chemistry, Journal Year: 2018, Volume and Issue: 376(3)

Published: April 13, 2018

Traditionally employed in the synthesis of small ring systems and rearrangement chemistry, sulfur-based ylides occupy a unique position toolbox synthetic organic chemist. In recent years number pioneering researchers have looked to expand application these unorthodox reagents through use transition metal catalysis. The strength flexibility such combination been shown be key importance developing powerful novel methodologies. This chapter summarises developments metal-catalysed sulfonium/sulfoxonium ylide reactions, as well providing historical perspective. overviewing successes this area, authors hope encourage others into growing field.

Language: Английский

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Application of arylsulfonium salts as arylation reagents

Tetrahedron Letters, Journal Year: 2017, Volume and Issue: 59(4), P. 299 - 309

Published: Dec. 6, 2017

Language: Английский

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Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle–Kirmse Reaction of α-Diazo Pyrazoleamides

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(9), P. 3299 - 3305

Published: Feb. 14, 2018

Although high enantioselectivity of [2,3]-sigmatropic rearrangement sulfonium ylides (Doyle–Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty fine discrimination heterotopic lone pairs sulfur chirality inversion at ylides. Here, we show that synergistic merger new α-diazo pyrazoleamides a N,N′-dioxide-nickel(II) complex catalyst enables highly enantioselective Doyle–Kirmse reaction. The pyrazoleamide substituent serves as both an activating directing group for ready formation metal-carbene- Lewis-acid-bonded ylide intermediate assistance dual-tasking nickel(II) complex. An alternative pathway greatly improves product enantiopurity even reaction symmetric diallylsulfane. majority transformations over series aryl- or vinyl-substituted pyrazoleamindes sulfides proceed rapidly (within 5–20 min most cases) with excellent results (up 99% yield 96% ee), providing breakthrough

Language: Английский

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Asymmetric Catalytic [2,3] Stevens and Sommelet–Hauser Rearrangements of α‐Diazo Pyrazoleamides with Sulfides

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(38), P. 13492 - 13498

Published: July 23, 2019

Abstract Catalytic enantioselective [2,3] Stevens and Sommelet–Hauser rearrangements of α‐diazo pyrazoleamides with sulfides were achieved by utilizing chiral N , ′‐dioxide/nickel( II ) complex catalysts. These proceeded well under mild reaction conditions, providing rapid facile access to a series functionalized 1,6‐dicarbonyls or sulfane‐substituted phenylacetates high excellent enantioselectivities. The catalytic system shows stereocontrol, discriminating between the heterotopic lone pairs sulfur controlling both 1,3‐proton transfer [2,3]‐σ rearrangement.

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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Tryptamine Synthesis by Iron Porphyrin Catalyzed C−H Functionalization of Indoles with Diazoacetonitrile

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(11), P. 3630 - 3634

Published: Dec. 20, 2018

Abstract The functionalization of C−H bonds with non‐precious metal catalysts is an important research area for the development efficient and sustainable processes. Herein, we describe iron porphyrin catalyzed reactions diazoacetonitrile N‐heterocycles yielding precursors tryptamines, along experimental mechanistic studies proof‐of‐concept enzymatic process YfeX enzyme. By using readily available FeTPPCl, achieved highly indole indazole heterocycles. These transformations feature mild reaction conditions, excellent yields broad functional group tolerance, can be conducted on gram scale, thus provide a unique streamlined access to tryptamines.

Language: Английский

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