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

Chemical Society Reviews, Год журнала: 2022, Номер 51(7), С. 2759 - 2852

Опубликована: Янв. 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

Язык: Английский

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Oxygen‐Linked Cyclopentadienyl Rhodium(III) Complexes‐Catalyzed Asymmetric C−H Arylation of Benzo[h]quinolines with 1‐Diazonaphthoquinones

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(28), С. 15510 - 15516

Опубликована: Апрель 16, 2021

Abstract Chiral cyclopentadienyl rhodium (CpRh) complex‐catalyzed asymmetric C−H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C‐linked and often synthetically challenging. To address these issues, we developed novel class of tunable bearing oxygen linkers, which were efficient catalysts for arylation benzo[ h ]quinolines with 1‐diazonaphthoquinones, affording axially heterobiaryls excellent yields enantioselectivity (up 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that reaction is likely proceed by electrophilic activation, followed coupling cyclometalated rhodium(III) complex 1‐diazonaphthoquinones.

Язык: Английский

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Enantioselective Synthesis of Five-Membered-Ring Atropisomers with a Chiral Rh(III) Complex

Organic Letters, Год журнала: 2020, Номер 22(23), С. 9199 - 9202

Опубликована: Ноя. 13, 2020

Axially chiral atropisomeric compounds are widely applied in asymmetric catalysis and medicinal chemistry, efficient methods for their synthesis high demand. This applies particular to atropisomers derived from five-membered aromatic rings because lower barrier rotation among the biaryl axis limits synthesis. We report here an enantioselective C–H functionalization method using our RhJasCp complex of atropisomer types that can be accessed three different five-membered-ring heterocycles.

Язык: 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, Год журнала: 2021, Номер 16(5), С. 443 - 459

Опубликована: Янв. 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.

Язык: Английский

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Rh(iii)-Catalyzed straightforward arylation of 8-methyl/formylquinolines using diazo compounds

Chemical Communications, Год журнала: 2019, Номер 55(48), С. 6886 - 6889

Опубликована: Янв. 1, 2019

A straightforward Rh(iii)-catalyzed general strategy was developed for the introduction of naphthol/phenol moieties to 8-methyl and formylquinolines using diazonaphthalen-2(1H)-ones/quinone diazides.

Язык: Английский

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An unusual reaction mode of 1-phenylpyrazolidinones toward diazonaphthalen-2(1H)-ones featuring cascade C(sp²)–H and C(sp³)–H bond cleavage

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(13), С. 3238 - 3243

Опубликована: Янв. 1, 2021

Herein, a novel synthesis of pyrazolidinone fused 1,3-benzooxazepine derivatives via formal [4 + 3] annulation reaction 1-phenylpyrazolidinones with diazonaphthalen-2(1H)-ones is presented.

Язык: Английский

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Transition‐Metal‐Catalyzed C−H Bond Functionalization of Arenes/Heteroarenes via Tandem C−H Activation and Subsequent Carbene Migratory Insertion Strategy

The Chemical Record, Год журнала: 2021, Номер 21(12), С. 4088 - 4122

Опубликована: Окт. 14, 2021

Abstract The past decade has witnessed tremendous developments in transition‐metal‐catalyzed C−H bond activation and subsequent carbene migratory insertion reactions, thus assisting the construction of diverse arene/heteroarene scaffolds. Various transition‐metal catalysts serve this purpose provide efficient pathways for an easy access to substituted heterocycles. A brief introduction metal‐carbenes been provided along with key mechanistic underlying coupling reactions. review is a concise knowledge about directing group‐assisted varied arenes/heteroarenes acceptor‐acceptor/donor‐acceptor diazo compounds. also highlights synthesis various carbocycles fused heterocycles through pathways, via C−C, C−N C−O forming mechanism usually involves process, followed by leading coupling.

Язык: Английский

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Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(22), С. 9027 - 9046

Опубликована: Май 8, 2019

Reactivity study of novel metal carbene complexes can offer new opportunities in catalytic transfer reactions as well other synthetic protocols. Metal with quinoid (QC) ligands are assumed to be key intermediates a variety metal-catalyzed QC using diazo quinones, which demands development the chemistry characterized metal–QC complexes. Herein we report isolation and ruthenium porphyrins [Ru(Por)(QC)] contribute first examples (i) structurally complex (by X-ray crystallography) (ii) isolated that undergoes reaction. The were prepared from reaction [Ru(Por)(CO)] quinones exhibited dual reactivity, i.e., hydrogen atom (HAT) transfer. stoichiometric these Ru–QC nitrosoarenes (ArNO) afforded nitrones up 90% yield, corresponding also developed. Both for series bearing electron-donating -withdrawing substituents showed reverse substituent effect on reactivity. Complexes reactive toward C–H X–H (X = N, S) bonds catalyze aerobic oxidation 1,4-cyclohexadiene; their HAT unsaturated hydrocarbons gave product yields 88%. unique reactivity electronic feature studied by spectroscopic means density functional theory (DFT) calculations.

Язык: Английский

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Rhodium‐Catalyzed Selective C−H Bond Functionalization of Quinolines

Asian Journal of Organic Chemistry, Год журнала: 2020, Номер 9(10), С. 1502 - 1518

Опубликована: Авг. 6, 2020

Abstract In the last two decades, rhodium‐based catalysts have been used extensively for sp 2 and 3 C−H bond activation/functionalization of various arenes, heteroarenes, aliphatic compounds, respectively. For quinoline functionalization rhodium has significantly as compared to other transition metals such cobalt, copper, ruthenium, palladium iridium. this Minireview progress on rhodium‐catalyzed selective N ‐oxides 8‐methylquinolines via activation, respectively highlighted. The main focus is reaction mechanism, substrate scope, positional selectivity.

Язык: Английский

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Synthesis of N-Arylindoles from 2-Alkenylanilines and Diazonaphthalen-2(1H)-ones through Simultaneous Indole Construction and Aryl Introduction

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(11), С. 7392 - 7404

Опубликована: Май 20, 2022

In this paper, an efficient synthesis of N-arylindoles through the cascade reaction 2-alkenylanilines with diazonaphthalen-2(1H)-ones is presented. Mechanistically, involves generation a Ru-carbene complex from diazonaphthalen-2(1H)-one, followed by carbene N-H bond insertion 2-alkenylaniline, intramolecular cyclization, and oxidative aromatization. reaction, Ru(II) acts as multifunctional catalyst to promote not only formation but also cyclization dehydrogenative Meanwhile, air green cost-effective oxidant. To our knowledge, first example in which were synthesized simultaneous introduction N-aryl unit construction indole scaffold. Notable advantages method include readily accessible halide-free substrates, additive-free conditions, good efficiency, excellent atom economy, compatibility diverse functional groups. addition, utility product thus obtained was showcased its structural transformations.

Язык: Английский

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