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, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

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Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2759 - 2852

Published: Jan. 1, 2022

C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have devoted transition-metal-catalyzed direct transformations of Metal carbenes generated in situ from transition-metal compounds diazo or its equivalents are usually applied the transient reactive intermediates furnish catalytic cycle for new C-C C-X bond formation. Using this strategy unactivated simple alkanes complex molecules can be further functionalized transformed multi-functionalized compounds. In area, carbene insertion bonds paid continuous attention. Diverse catalyst design strategies, synthetic methods, potential applications developed. This critical review will summarize advance dated up July 2021, by categories aliphatic C(sp3)-H, aryl (aromatic) C(sp2)-H, heteroaryl (heteroaromatic) C(sp2)-H bonds, alkenyl alkynyl C(sp)-H, well asymmetric more coverage given recent work. Due rapid development future directions topic also discussed. give authors an overview chemistry with focus on systems

Language: Английский

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Recent advances in cobalt-catalysed C–H functionalizations

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(48), P. 10119 - 10141

Published: Jan. 1, 2019

Ready availability, low cost and toxicity of cobalt salts have redirected the attention researchers away from noble metals, such as Pd, Rh, Ir, towards Co in field C-H functionalization. In this context, examples Co-catalysed functionalization exponentially grown over last few decades. This present review focuses on most recent developments C(sp2)-H C(sp3)-H functionalizations. Included is also a comprehensive overview enantioselective transformations.

Language: Английский

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Cp*Co(III)-Catalyzed C–H Acylmethylation of Arenes by Employing Sulfoxonium Ylides as Carbene Precursors

Organic Letters, Journal Year: 2018, Volume and Issue: 20(18), P. 5981 - 5984

Published: Sept. 12, 2018

A Cp*Co(III)-catalyzed C-H bond functionalization of a range arenes by employing sulfoxonium ylides as carbene precursors instead diazo compounds and other has been established. This reaction is highly efficient without any additive, possesses high step atom economies, tolerates functional groups.

Language: Английский

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Cobalt‐Catalyzed C(sp³)−H Functionalization Reactions

Asian Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 7(7), P. 1193 - 1205

Published: May 14, 2018

Abstract C−H functionalization reactions hold great potential for the streamlined synthesis of complex molecules and are currently a “hot” topic in organic synthesis. Among various transition metals that have been used, cobalt has recently attracted increased attention as catalyst reactions, owing to its ready availability high reactivity. Although number cobalt‐catalyzed C(sp 2 )−H reported date, 3 remain challenging. This Focus Review summarizes recent progress involve activation form organometallic intermediates.

Language: Английский

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C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(83), P. 10827 - 10841

Published: Jan. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Language: Английский

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Co(III), Rh(III) & Ir(III)‐Catalyzed Direct C−H Alkylation/Alkenylation/Arylation with Carbene Precursors

Chemistry - An Asian Journal, Journal Year: 2021, Volume and Issue: 16(5), P. 443 - 459

Published: Jan. 15, 2021

Metal carbenes play a pivotal role in transition-metal-catalyzed synthetic transfer reactions. The metal carbene is generated either from diazo compound through facile extrusion of N2 with catalyst or situ other sources like triazoles, pyriodotriazoles, sulfoxonium ylides and iodonium-ylide. On the hand, Co(III), Rh(III) & Ir(III)-catalyzed C-H functionalizations have been well established as key step to enable construction various transformations. Interestingly, recent years, merging these two concepts activation migratory insertion gained much attention, particular group 9 metal-catalyzed arene precursors via insertion. In this review, we summarize advances direct alkylation/alkenylation/arylation also discuss intermediates within catalytic cycles.

Language: Английский

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Rhodium(iii)-catalyzed regio- and stereoselective benzylic α-fluoroalkenylation with gem-difluorostyrenes

Chemical Communications, Journal Year: 2017, Volume and Issue: 53(74), P. 10326 - 10329

Published: Jan. 1, 2017

Rhodium(iii)-catalyzed mild benzylic α-fluoroalkenylation of 8-methylquinolines with gem-difluorostyrenes has been developed. This reaction occurred via C-H activation and C-F cleavage is applicable to a wide range substrates, leading the synthesis Z-alkenyl fluorides under redox-neutral conditions high regio- stereoselectivity.

Language: Английский

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Cp*Co^III–Catalyzed Alkylation of Primary and Secondary C(sp³)-H Bonds of 8-Alkylquinolines with Maleimides

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(3), P. 1542 - 1552

Published: Jan. 8, 2019

The cobalt(III)-catalyzed C(sp3)-H bond alkylation of 8-methyl quinoline with maleimides is reported. In contrast to the rhodium-catalyzed method, in current cobalt-catalyzed a catalytic amount acid used, and importantly, it also applicable secondary alkylation. developed methodology for N-alkyl- N-aryl-substituted unsubstituted maleimides, tolerates variety functional groups on moiety. Atom-economy high regioselectivity good excellent yields alkylated products under mild reaction conditions are important features this method.

Language: Английский

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