Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants DOI
Sabyasachi Bhunia, Partha Ghosh,

Snigdha Rani Patra

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(18), P. 3664 - 3708

Published: May 11, 2020

Abstract Since the beginning of this century, homogeneous gold‐catalyzed alkyne transformations have been an active area research in pursuit developing efficient synthetic methodologies. This emerging which at exploited mild Lewis acid character gold and its propensity to form π‐complex with alkyne, has reinvigorated upon discovery oxidative functionalization 2007. The oxidation enabled direct access α‐oxo carbenes alkynal complex versatile reactivity applied achieve including but not limited oxyarylation, C−H, X−H (X=N, O) insertion, cyclization, cycloaddition, ring expansion, various cascade reactions. review provides a comprehensive summary methods, applications mechanistic insight by N−O/S−O/C−O bond oxidants covering literature reports appeared since magnified image

Language: Английский

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts DOI Creative Commons
Daniel Kaiser, Immo Klose,

Rik Oost

et al.

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

Citations

698
Blue‐Light‐Induced Carbene‐Transfer Reactions of Diazoalkanes DOI
Renè Hommelsheim, Yujing Guo, Zhen Yang

et al.

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

Citations

241
Lightening Diazo Compounds? DOI Creative Commons
Jakub Durka, Joanna Turkowska, Dorota Gryko

et al.

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

Citations

177
Synthetic Applications of Sulfonium Salts DOI Creative Commons
S.I. Kozhushkov, Manuel Alcarazo

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

Citations

164
Recent Perspectives on Rearrangement Reactions of Ylides via Carbene Transfer Reactions DOI Creative Commons
Sripati Jana, Yujing Guo, René M. Koenigs

et al.

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

Citations

139
Rh(III)-Catalyzed Cascade Reactions of Sulfoxonium Ylides with α-Diazocarbonyl Compounds: An Access to Highly Functionalized Naphthalenones DOI
Xi Chen, Muhua Wang, Xinying Zhang

et al.

Organic Letters, Journal Year: 2019, Volume and Issue: 21(8), P. 2541 - 2545

Published: April 8, 2019

An unprecedented cascade reaction of benzoyl sulfoxonium ylides with α-diazocarbonyl compounds leading to the formation highly functionalized naphthalenones containing a β-ketosulfoxonium ylide moiety is presented. Promisingly, naphthalenone derivative thus obtained was found be versatile intermediate toward diversely naphthalene derivatives including substituted 1-naphthol, 2-hydroxynaphthalen-1(2H)-one, naphthalen-1,2-dione, and 2-(methylsulfinyl)naphthalen-1-ol.

Language: Английский

Citations

133
Sulfilimines as Versatile Nitrene Transfer Reagents: Facile Access to Diverse Aza‐Heterocycles DOI
Xianhai Tian,

Lina Song,

Matthias Rudolph

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(11), P. 3589 - 3593

Published: Jan. 2, 2019

Abstract We herein report the unprecedented synthesis of diverse biologically important aza‐heterocycles by employing sulfilimines as nitrene transfer reagents. This class sulfur‐based aza‐ylides had not been successfully used for gold before. work contains an efficient generation α‐imino carbenes N−S cleavage sulfilimines. These undergo C−H insertion, cyclopropanation, and nucleophilic attack to form indoles (44 examples), 3‐azabicyclo[3.1.0]hexan‐2‐imines (24 imidazoles (3 examples). Our study represents a unique gold‐catalyzed reaction between alkynes sulfur ylides, also includes first aza‐heterocycle that proceeds intermolecular followed cyclopropanation carbenes. Moreover, unexpected 4‐acylquinolines examples) from 2‐acylphenyl propargylic silyl ether derivatives 1,2‐hydride shift onto carbene subsequent Mukaiyama aldol cyclization was discovered.

Language: Английский

Citations

132
A leap forward in sulfonium salt and sulfur ylide chemistry DOI
Rong Fan, Chen Tan, Yongguo Liu

et al.

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

Published: June 3, 2020

Language: Английский

Citations

119
Sulfoxonium ylides: simple compounds with chameleonic reactivity DOI
Giorgiana Denisa Bisag, Silvia Ruggieri, Mariafrancesca Fochi

et al.

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(43), P. 8793 - 8809

Published: Jan. 1, 2020

Sulfur ylides first disclosed in 1930 started to gain more attention the 1960s, thanks mainly studies by Corey and Chaykovsky on their use for preparation of strained rings. More recently, chemistry these compounds has experienced important growth, part due similarity reactivities with diazo compounds. This short review provides an overview great assortment reactions sulfoxonium ylides, outlining a comparison between congeners: sulfonium Insertion reactions, cyclisation ring-opening are highlighted, giving particular catalytic asymmetric methodologies.

Language: Английский

Citations

115
α‐Imino Gold Carbene Intermediates from Readily Accessible Sulfilimines: Intermolecular Access to Structural Diversity DOI Creative Commons
Xianhai Tian,

Lina Song,

A. Stephen K. Hashmi

et al.

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(15), P. 3197 - 3204

Published: Dec. 3, 2019

Abstract Catalytic approaches to pharmaceutically important bioactive skeletons through gold carbene intermediates have experienced a dramatic development in the last decade. Although various precursors continue play an role heterocyclic syntheses, these reagents are associated with some drawbacks terms of functional group tolerance, synthetic methods and safety limitations. A new generation nitrene transfer was established 2019: sulfilimines. These safe, inexpensive readily available. They can conveniently be stored handled, thus represent ideal for fast modular modification scaffolds preparation libraries by intermolecular reactions two components. Both practical synthesizing sulfilimines versatility ylidic species gold‐catalyzed structural diversity, both heterocycles carbocycles, will outlined this Concept article.

Language: Английский

Citations

111