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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Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(23), P. 13810 - 13889

Published: Nov. 1, 2017

Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals area is expanding scope coupling partners. In past decade, diazo compounds (or their precursors N-tosylhydrazones) emerged nucleophilic partners C-C single bond or C═C double formations transition-metal-catalyzed reactions. This type reaction involves following general steps. First, organometallic species generated by various processes, including oxidative addition, transmetalation, cyclization, cleavage, and C-H activation. Subsequently, reacts with substrate to generate metal carbene intermediate, which undergoes rapid migratory insertion form a bond. The new from may undergo transformations. carbene-based has proven be general: transition metals Pd, Cu, Rh, Ni, Co, Ir are effective catalysts; also extended substrates other than compounds; cascade processes devised based on insertion. review will summarize achievements made this field since 2001.

Language: Английский

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Sulfoxonium Ylides as a Carbene Precursor in Rh(III)-Catalyzed C–H Acylmethylation of Arenes

Organic Letters, Journal Year: 2017, Volume and Issue: 19(19), P. 5256 - 5259

Published: Sept. 13, 2017

Sulfoxonium ylides act as an efficient carbene precursor in rhodium(III)-catalyzed C-H acylmethlyation of a variety arenes assisted by different chelating groups, and both aryl- alkyl-substituted β-carbonyl sulfoxonium are applicable. The system proceeded under redox-neutral conditions with broad scope, high efficiency, functional group tolerance.

Language: Английский

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Recent Advances in Reactions Using Enaminone in Water or Aqueous Medium

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(9), P. 1508 - 1521

Published: April 8, 2022

Abstract Enaminones have in the past decade received renewed interest organic synthesis by acting as highly versatile building blocks. Particularly, featured amino and carbonyl group enaminone structure endow them with ability of tolerating water via hydrogen bonding effect. Thus, designing synthetic methods aqueous medium enaminones main blocks has extensive attention notable success. Based on our longstanding efforts interests chemistry, we review herein research advances participated medium. magnified image

Language: Английский

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Recent advances in visible light-mediated chemical transformations of enaminones

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(2), P. 108977 - 108977

Published: Aug. 26, 2023

Language: Английский

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Rhodium(III)-Catalyzed Synthesis of Naphthols via C–H Activation of Sulfoxonium Ylides

Organic Letters, Journal Year: 2017, Volume and Issue: 19(16), P. 4307 - 4310

Published: Aug. 7, 2017

Direct and efficient synthesis of 1-naphthols has been realized via Rh(III)-catalyzed C-H activation sulfoxonium ylides subsequent annulation with alkynes, where the ylide functioned as a new traceless bifunctional directing group. This reaction occurred under redox-neutral conditions broad substrate scope.

Language: Английский

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Nitrone Directing Groups in Rhodium(III)‐Catalyzed C−H Activation of Arenes: 1,3‐Dipoles versus Traceless Directing Groups

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(49), P. 15351 - 15355

Published: Nov. 10, 2016

Abstract Functionalizable directing groups (DGs) are highly desirable in C−H activation chemistry. The nitrone DGs explored rhodium(III)‐catalyzed of arenes and couplings with cyclopropenones. N‐tert ‐butyl nitrones bearing a small ortho substituent coupled to afford 1‐naphthols, where the acts as traceless DG. In contrast, coupling bulky group follows acylation/[3+2] dipolar addition pathway give bicyclics. N‐arylnitrones same process but delivers different

Language: Английский

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Cobalt(III)- and Rhodium(III)-Catalyzed C–H Amidation and Synthesis of 4-Quinolones: C–H Activation Assisted by Weakly Coordinating and Functionalizable Enaminone

Organic Letters, Journal Year: 2017, Volume and Issue: 19(7), P. 1812 - 1815

Published: March 30, 2017

Cobalt(III) and rhodium(III) catalysts exhibited complementary scope in C–H amidation of aryl enaminones. The reactions proceeded with broad under the assistance a weakly coordinating bifunctional enaminone directing group. electrophilicity group can be further utilized subsequent hydrolysis–cyclization to afford NH 4-quinolones telescoping reactions.

Language: Английский

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Propargyl Alcohols as One-Carbon Synthons: Redox-Neutral Rhodium(III)-Catalyzed C–H Bond Activation for the Synthesis of Isoindolinones Bearing a Quaternary Carbon

Organic Letters, Journal Year: 2017, Volume and Issue: 19(6), P. 1294 - 1297

Published: Feb. 28, 2017

Herein, rhodium(III)-catalyzed C–H activation/subsequent [4 + 1] cyclization reactions between benzamides and propargyl alcohols are reported in which serve as unusual one-carbon units. This title transformation led to a series of isoindolinones bearing quaternary carbon with moderate good yields without the requirement for external metal oxidants. Due mild simple reaction conditions, this is compatible various functional groups.

Language: Английский

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Direct Access to Cobaltacycles via C–H Activation: N-Chloroamide-Enabled Room-Temperature Synthesis of Heterocycles

Organic Letters, Journal Year: 2017, Volume and Issue: 19(19), P. 5348 - 5351

Published: Sept. 19, 2017

Cobaltacycle synthesis via C-H activation has been achieved for the first time, providing key mechanistic insight into cobalt catalytic chemistry. N-Chloroamides are used as a directing synthon cobalt-catalyzed room-temperature and construction of heterocycles. Alkynes coupling partners allow convenient access to isoquinolones, class synthetically pharmaceutically important compounds. The broad substrate scope enables diverse range substitution patterns be incorporated heterocyclic scaffold.

Language: Английский

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