A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Language: Английский

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Rhodium(iii)-catalyzed chemodivergent annulations between N-methoxybenzamides and sulfoxonium ylides via C–H activation

Chemical Communications, Journal Year: 2018, Volume and Issue: 54(6), P. 670 - 673

Published: Jan. 1, 2018

Rhodium-catalyzed and acid-controlled chemodivergent annulations between N-methoxybenzamides sulfoxonium ylides have been realized.

Language: Английский

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Enantioselective Synthesis of Chiral‐at‐Sulfur 1,2‐Benzothiazines by Cp^xRh^III‐Catalyzed C−H Functionalization of Sulfoximines

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15539 - 15543

Published: Oct. 10, 2018

Abstract Sulfoximines with stereogenic sulfur atoms are attractive structural motifs in drug discovery. A direct catalytic enantioselective method for the synthesis of sulfur‐chiral 1,2‐benzothiazines from readily accessible diaryl sulfoximines is presented. Rhodium(III) complexes equipped chiral cyclopentadienyl ligands and paired suitable carboxylic acid additives engage an enantiodetermining C−H activation directed by sulfoximine group. Subsequent trapping rhodacycle a broad range diazoketones gives access to S‐chiral synthetically highly substitution patterns good yields enantioselectivities.

Language: Английский

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Rhodium-Catalyzed Relay Carbenoid Functionalization of Aromatic C–H Bonds toward Fused Heteroarenes

Organic Letters, Journal Year: 2018, Volume and Issue: 20(5), P. 1396 - 1399

Published: Feb. 22, 2018

A rhodium-catalyzed annulation between ethyl benzimidates and α- aroyl sulfur ylides was developed, affording a series of pyrano[4,3,2-ij]isoquinoline derivatives in moderate to good yields with functional group compatibility. The procedure featured dual ortho-C–H functionalization cyclization one pot. optoelectronic properties those fused heteroarenes were tested by UV/vis fluorescence spectrometers.

Language: Английский

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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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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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Synthesis of indoles and quinazolines via additive-controlled selective C–H activation/annulation of N-arylamidines and sulfoxonium ylides

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(28), P. 4039 - 4042

Published: Jan. 1, 2019

Selective synthesis of indoles and quinazolines was achieved through a precise control C–H activation/annulation by changing additives.

Language: Английский

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Synthesis of (2H)-Indazoles through Rh(III)-Catalyzed Annulation Reaction of Azobenzenes with Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 83(7), P. 4070 - 4077

Published: March 16, 2018

The rhodium(III)-catalyzed C–H functionalization followed by intramolecular annulation reactions between azobenzenes and sulfoxonium ylides is described. This protocol leads to the efficient formation of 3-acyl (2H)-indazoles with a range substrate scope. A high level chemoselectivity functional group tolerance this transformation were also observed.

Language: Английский

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Rhodium(III)-Catalyzed Imidoyl C–H Activation for Annulations to Azolopyrimidines

Organic Letters, Journal Year: 2018, Volume and Issue: 20(8), P. 2464 - 2467

Published: March 27, 2018

Azolopyrimidines are efficiently prepared by direct imidoyl C–H bond activation. Annulations of N-azolo imines with sulfoxonium ylides and diazoketones under redox-neutral conditions alkynes oxidizing provide products various arrangements nitrogen atoms carbon substituents. We have also probed the mechanism this first example Rh(III)-catalyzed activation structural characterization a catalytically competent rhodacycle obtained after kinetic isotope effects.

Language: Английский

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