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

Chemical Reviews, Год журнала: 2017, Номер 117(23), С. 13810 - 13889

Опубликована: Ноя. 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.

Язык: Английский

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Annulative π-Extension (APEX): Rapid Access to Fused Arenes, Heteroarenes, and Nanographenes

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(37), С. 11144 - 11164

Опубликована: Март 30, 2017

The annulative π-extension (APEX) reaction has the potential to have a tremendous impact on fields of materials science and bioimaging, as well pharmaceutical/agrochemical industries, since it allows access fused aromatic systems from relatively simple compounds in single step. Typically, an APEX facilitates one-pot without need prefunctionalize compounds. This advantageous feature is extremely useful for tuning modifying molecular properties last step synthesis. In this Review, progress applications reactions unfunctionalized arenes heteroarenes are described.

Язык: Английский

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Diazo Compounds: Versatile Synthons for the Synthesis of Nitrogen Heterocycles via Transition Metal‐Catalyzed Cascade C–H Activation/Carbene Insertion/Annulation Reactions

Advanced Synthesis & Catalysis, Год журнала: 2018, Номер 361(5), С. 919 - 944

Опубликована: Ноя. 27, 2018

Abstract This review covers some unique diazo compounds, the coupling partners to access various versatile functionalized nitrogen heterocycles, such as indoles, indolines, isoquinolines, isoquinolones, and so on. Different transition metals (such Rh, Pd, Ru, Ir, Cu, Co) are involved in these transformations, which involve consecutive processes: metal‐catalyzed cascade C–H activation/carbene insertion/intramolecular annulation. magnified image

Язык: Английский

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Polycyclic Arene Synthesis by Annulative π-Extension

Journal of the American Chemical Society, Год журнала: 2018, Номер 141(1), С. 3 - 10

Опубликована: Ноя. 5, 2018

Annulative π-extension (APEX) has emerged as a powerful and efficient synthetic method for the construction of polycyclic aromatic hydrocarbons, nanographenes, π-extended fused heteroarenes. In contrast to classical multistep syntheses requiring substrate prefunctionalization, APEX reactions minimize number preparative steps by direct C–H activation small templates. this Perspective, we review recently reported shed light on utility, scope, promise approach next-generation arenes.

Язык: Английский

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Selective Synthesis of Indoles by Cobalt(III)-Catalyzed C–H/N–O Functionalization with Nitrones

ACS Catalysis, Год журнала: 2016, Номер 6(4), С. 2705 - 2709

Опубликована: Фев. 29, 2016

The redox-neutral annulation of alkynes by differently decorated nitrones set the stage for a step-economical access to indoles with ample substrate scope. C–H/N–O functionalization process proceeded through kinetically relevant C–H activation carboxylate assistance, and displayed an excellent site- regio-selectivity unsymmetrical alkynes.

Язык: Английский

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Access to Structurally Diverse Quinoline-Fused Heterocycles via Rhodium(III)-Catalyzed C–C/C–N Coupling of Bifunctional Substrates

Organic Letters, Год журнала: 2016, Номер 18(12), С. 2812 - 2815

Опубликована: Июнь 7, 2016

Rhodium(III)-catalyzed C-H activation of heteroarenes and functionalization with bifunctional substrates such as anthranils allows facile construction quinoline-fused heterocycles under redox-neutral conditions. The couplings feature broad substrate scope provide step-economical access to two classes condensed heterocycles.

Язык: Английский

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Ruthenium(II)‐Catalyzed C−H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate‐Controlled Synthesis of Indoles and 3H‐Indoles

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(39), С. 11877 - 11881

Опубликована: Авг. 25, 2016

Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed afforded NH indoles 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters by cleavage the C(N2 )-C(acyl) bond whereas α-diazomalonates gave C-N cleavage. This reaction constitutes first intermolecular substrates with arenes ruthenium-catalyzed C-H activation.

Язык: Английский

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Regio-selective synthesis of diversely substituted benzo[a]carbazoles through Rh(iii)-catalyzed annulation of 2-arylindoles with α-diazo carbonyl compounds

Chemical Communications, Год журнала: 2016, Номер 53(7), С. 1297 - 1300

Опубликована: Дек. 22, 2016

A novel synthetic approach toward benzo[a]carbazoles or 6-amino containing an unprotected NH unit through Rh(iii)-catalyzed cascade reactions of 2-arylindoles 2-arylindole-3-carbonitriles with α-diazo carbonyl compounds has been established. To our knowledge, this is the first example in which indole used as a directing group for intramolecular C(sp2)-H bond functionalization to give benzo[a]carbazole derivatives. Notably, method features easily obtainable substrates, good functional tolerance, excellent regio-selectivity, and high atom-efficiency.

Язык: Английский

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Catalyst‐Controlled Regiodivergent Alkyne Insertion in the Context of C−H Activation and Diels–Alder Reactions: Synthesis of Fused and Bridged Cycles

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(28), С. 8163 - 8167

Опубликована: Май 17, 2017

Abstract Rhodium(III)‐ and cobalt(III)‐catalyzed C−H activation of indoles coupling with 1,6‐enynes is discussed. Under rhodium(III) catalysis, the alkyne insertion follows 2,1‐regioselectivity a subsequent type‐I intramolecular Diels–Alder reaction (IMDA) to afford [6,5]‐fused cycles. When catalyzed by cobalt(III) congener, 1,2‐insertion preferred, followed rare type‐II IMDA, thus leading bridged [3,3,1]‐cycles. This selectivity was mainly tuned steric sensitivity catalyst.

Язык: Английский

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Tandem Rh(III)-Catalyzed C–H Amination/Annulation Reactions: Synthesis of Indoloquinoline Derivatives in Water

Organic Letters, Год журнала: 2016, Номер 18(12), С. 2820 - 2823

Опубликована: Июнь 7, 2016

An efficient Rh(III)-catalyzed synthetic method for indoloquinoline derivatives from readily available indoles and isoxazoles was developed. This annulation procedure undergoes tandem C–H activation, cyclization, condensation steps. In this domino cyclization reaction, water is an solvent. A catalytically competent five-membered rhodacycle has been isolated characterized, thus revealing a key intermediate in the catalytic cycle.

Язык: Английский

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