Rh(III)-Catalyzed Cascade Reactions of Sulfoxonium Ylides with α-Diazocarbonyl Compounds: An Access to Highly Functionalized Naphthalenones

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

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Selective Synthesis of Benzo[a]Carbazoles and Indolo[2,1‐a]‐Isoquinolines via Rh(III)‐Catalyzed C−H Functionalizations of 2‐Arylindoles with Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Journal Year: 2018, Volume and Issue: 360(19), P. 3781 - 3787

Published: July 12, 2018

Abstract A highly chem‐ and regioselective synthesis of diversely substituted benzo[ a ]carbazoles indolo[2,1‐ ]‐isoquinolines through Rh(III)‐catalyzed cascade reactions 2‐arylindoles with sulfoxonium ylides is presented. To be specific, treatment 2‐arylindoles, 2‐arylindole‐3‐carbaldehydes, 2‐arylindole‐3‐carbonitriles or 2‐aryl‐3‐methylindoles under the catalysis Rh(III) led to selective formation 6‐aryl/alkyl ]carbazoles, 5‐acylbenzo[ 6‐amino‐5‐acylbenzo[ 12‐methylindolo[2,1‐ ]isoquinolines, respectively. Mechanistically, title compounds involves process including metalation inert C( sp 2 )−H bond, migratory insertion ylide into carbon‐metal bond via an in situ carbenoid formation, protodemetalation, condensation. our knowledge, this first example which β‐carbonyl were used as stable carbene precursors bifunctional C2 synthons afford ]isoquinolines. magnified image

Language: Английский

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Cp*M-Catalyzed Direct Annulation with Terminal Alkynes and Their Surrogates for the Construction of Multi-Ring Systems

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(17), P. 9747 - 9757

Published: Aug. 3, 2020

Transition-metal-catalyzed C–H activation followed by oxidative cyclization with unsaturated coupling partners has been a valuable synthetic tool for the multiring molecular scaffolds. This Perspective introduces recent progress on Cp*M-catalyzed (M = Co, Rh, and Ir) direct annulation of functionalized arenes terminal alkynes their equivalents through bond cleavage. The highlighted examples are categorized according to 10 different types reagents used in transformations. representative conditions, selected reaction scope, key mechanistic aspects briefly summarized.

Language: Английский

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Sulfoxonium Ylide Derived Metal Carbenoids in Organic Synthesis

Synthesis, Journal Year: 2018, Volume and Issue: 51(03), P. 612 - 628

Published: Dec. 12, 2018

As pioneered by Corey and Chaykovsky, sulfoxonium ylides have had widespread application in organic synthesis for more than a half century. In most of the reactions, were used to react with electrophiles. Under suitable reaction conditions these can generate metal carbenoids nucleophiles. By combining typical reactivity transition-metal catalysis, growing number investigations expanded their synthesis. This review provides an update on preparation applications carbenoid transfer reactions. 1 Introduction 2 Preparation Sulfoxonium Ylides 3 Investigation Carbenoid Formation from Ylide 4 X–H (X = N, O, S, C) Functionalization Reactions 5 Polymerizaton Carbenoids Generated 6 Conclusion Perspective

Language: Английский

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Ru^II-Catalyzed/NH₂-Assisted Selective Alkenyl C–H [5 + 1] Annulation of Alkenylanilines with Sulfoxonium Ylides to Quinolines

Organic Letters, Journal Year: 2019, Volume and Issue: 21(12), P. 4812 - 4815

Published: June 13, 2019

A novel ruthenium-catalyzed [5 + 1] annulation of 2-alkenylanilines with sulfoxonium ylides was developed for the rapid assembly highly functionalized quinolines. This new catalytic process employs challenging but synthetically ideal free amino functionality to achieve alkenyl C–H activation as one-carbon coupling partners. Various 2-acylquinolines could be obtained good yields and excellent functional group tolerance. Moreover, potential synthetic application this methodology exemplified by several chemical transformations.

Language: Английский

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Recent Applications of α-Carbonyl Sulfoxonium Ylides in Rhodium- and Iridium-Catalyzed C–H Functionalizations

Synlett, Journal Year: 2018, Volume and Issue: 30(01), P. 21 - 29

Published: Sept. 5, 2018

Sulfoxonium ylides are a special type of sulfur that serve as new C1 or C2 synthons recently developed for use in C–H functionalization to access acylmethylated cyclized compounds through the formation metal carbene species. Many excellent works have reported syntheses various useful skeletons from these versatile synthons. These developments not previously been completely investigated reviewed. In this review, we summarize recent advances α-carbonyl sulfoxonium functionalizations, including ortho-C–H acylmethylation reactions and activation/cyclization reactions. Table Contents 1 Introduction 2 Ortho-C–H Acylmethylation Reactions 3 Activation/Cyclization 3.1 Anilines Enamines 3.2 Azobenzenes 3.3 N-Methoxybenzamide 3.4 Imines 3.5 N-Azoloimines 3.6 Benzoylacetonitriles 3.7 Benzoyl Ylides 4 Conclusion

Language: Английский

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Rhodium-Catalyzed Reaction of Sulfoxonium Ylides and Anthranils toward Indoloindolones via a (4 + 1) Annulation

Organic Letters, Journal Year: 2019, Volume and Issue: 21(17), P. 6653 - 6657

Published: Aug. 19, 2019

A rhodium-catalyzed annulation between aroyl sulfoxonium ylides and anthranils has been developed to synthesize 10H-indolo[1,2-a]indol-10-one derivatives. This reaction started with an unpredented (4 + 1) toward N-(2-formylphenyl) indolones, proceeding the sequential ortho-amination of C–H bond in by insertion N–H carbene. Finally, Aldol condensation constructed second indole ring. procedure features formation two C–N bonds one C═C pot.

Language: Английский

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Rhodium(III)‐Catalyzed C‐H Activation of Benzoylacetonitriles and Cyclization with Sulfoxonium Ylides to Naphthols

Advanced Synthesis & Catalysis, Journal Year: 2018, Volume and Issue: 360(13), P. 2546 - 2551

Published: April 24, 2018

Abstract Rhodium(III)‐Catalyzed C−H activation of benzoylacetonitriles in coupling with sulfoxonium ylides was developed to synthesize diversified substituted naphthols, which aryl, heterocyclic and alkyl groups are tolerated. Intriguingly, we have further implemented transformation for 1‐naphthols give some intriguing fused tricyclic compounds derivatives propranolol, demonstrate the practical utility this methodology. magnified image

Language: Английский

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Ruthenium(ii)-catalyzed selective C–H bond activation of imidamides and coupling with sulfoxonium ylides: an efficient approach for the synthesis of highly functional 3-ketoindoles

Organic Chemistry Frontiers, Journal Year: 2019, Volume and Issue: 6(8), P. 1183 - 1188

Published: Jan. 1, 2019

Ruthenium-catalyzed selective C–H bond activation of imidamides and annulation sulfoxonium ylides were achieved, which afforded a series 3-ketoindole derivatives in good yields, with functional group compatibility.

Language: Английский

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Transition Metal Promoted Cascade Heterocycle Synthesis through C−H Functionalization

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(44), P. 9749 - 9783

Published: June 18, 2020

Sequential, domino and tandem reactions could be defined as a sequence of synthetic transformations that occur one after the other, in same reaction flask. This Review highlights recent advances at overlap two worlds: transition-metal mediated C-H activation trigger cascade reaction, for heterocycles synthesis. To shed some light on this intricate "middle-earth", focus was put mechanism rather than type metal or chronological order reaction. The aim is to separate, then highlight, true initiated by activation, compared other examples functionalization heterocycle syntheses.

Language: Английский

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