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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Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(25), С. 8304 - 8329

Опубликована: Окт. 12, 2018

Abstract In recent years, transition‐metal‐catalyzed C−H activation has become a key strategy in the field of organic synthesis. Rhodium complexes are widely used as catalysts variety functionalization reactions because their high reactivity and selectivity. The availability number rhodium various oxidation states enables diverse reaction patterns to be obtained. Regioselectivity, an important issue chemistry, can accomplished by using directing group assist reaction. However, obtain target functionalized compounds, it is also necessary use that easily removed. A wide range directed catalyzed have been reported date. this Review, we discuss Rh‐catalyzed aided removable such phenol, amine, aldehyde, ketones, ester, acid, sulfonic N‐heteroaromatic derivatives.

Язык: Английский

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Cross‐Coupling of α‐Carbonyl Sulfoxonium Ylides with C−H Bonds

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(42), С. 13117 - 13121

Опубликована: Авг. 29, 2017

Abstract The functionalization of carbon–hydrogen bonds in non‐nucleophilic substrates using α‐carbonyl sulfoxonium ylides has not been so far investigated, despite the potential safety advantages that such reagents would provide over either diazo compounds or their situ precursors. Described herein are cross‐coupling reactions with C(sp 2 )−H arenes and heteroarenes presence a rhodium catalyst. reaction proceeds by succession C−H activation, migratory insertion ylide into carbon–metal bond, protodemetalation, last step being turnover‐limiting. method is applied to synthesis benz[c]acridines when allied an iridium‐catalyzed dehydrative cyclization.

Язык: Английский

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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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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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C–F Bond Cleavage Enabled Redox-Neutral [4+1] Annulation via C–H Bond Activation

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(5), С. 1762 - 1765

Опубликована: Янв. 18, 2017

Using α,α-difluoromethylene alkyne as a nontraditional one-carbon reaction partner, synthetically novel method for the construction of isoindolin-1-one derivatives via Rh(III)-catalyzed [4+1] annulation is reported. The 2-fold C-F bond cleavage not only enables generation desired product under an overall oxidant-free condition but also results in net migration carbon-carbon triple bond. In addition, present protocol exhibits tolerance wide spectrum functional groups due to mild conditions employed.

Язык: Английский

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Palladium-Catalyzed Formal [4 + 1] Annulation via Metal Carbene Migratory Insertion and C(sp²)–H Bond Functionalization

ACS Catalysis, Год журнала: 2017, Номер 7(3), С. 1993 - 1997

Опубликована: Фев. 7, 2017

A highly efficient and operationally simple palladium-catalyzed formal [4 + 1] annulation reaction has been developed. The is featured by the formation of two different C–C bonds on a carbenic center. It represents concise method for synthesis wide range polycyclic aromatic hydrocarbons (PAHs) 1H-indenes with easily available (trimethylsilyl)diazomethane as carbene source. Metal migratory insertion C(sp2)–H bond activation are proposed key steps in this transformation. further demonstrates versatility carbene-based coupling combination various transition-metal-catalyzed transformations.

Язык: Английский

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Rh(III)-Catalyzed C–H Activation/Cyclization of Benzamides and Diazonaphthalen-2(1H)-ones for Synthesis of Lactones

Organic Letters, Год журнала: 2017, Номер 19(15), С. 4002 - 4005

Опубликована: Июль 20, 2017

A Rh(III)-catalyzed C–H activation/cyclization of benzamides and diazonaphthalen-2(1H)-ones for synthesis lactones has been developed. In the presence Rh(III) catalysis, would form rhodacycle species could be trapped by arylation, following intramolecular lactonization rapidly furnish products. Thus, were first revealed as a component in Rh(III)-catalysis, while kinetic isotope effect study was conducted plausible reaction mechanism proposed.

Язык: Английский

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Ruthenium(ii)-catalyzed selective C–H bond activation of imidamides and coupling with sulfoxonium ylides: an efficient approach for the synthesis of highly functional 3-ketoindoles

Organic Chemistry Frontiers, Год журнала: 2019, Номер 6(8), С. 1183 - 1188

Опубликована: Янв. 1, 2019

Ruthenium-catalyzed selective C–H bond activation of imidamides and annulation sulfoxonium ylides were achieved, which afforded a series 3-ketoindole derivatives in good yields, with functional group compatibility.

Язык: Английский

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Rh(III)-Catalyzed Chemodivergent Annulations between Indoles and Iodonium Carbenes: A Rapid Access to Tricyclic and Tetracyclic N-Heterocylces

Organic Letters, Год журнала: 2021, Номер 23(11), С. 4233 - 4238

Опубликована: Май 21, 2021

Herein, we report an acid-controlled highly tunable selectivity of Rh(III)-catalyzed [4 + 2] and [3 3] annulations N-carboxamide indoles with iodonium ylides lead to form synthetically important tricyclic tetracyclic N-heterocycles. Here, ylide serves as a carbene precursor. The protocol proceeds under operationally simple conditions provides novel scaffolds such 3,4-dihydroindolo[1,2-c]quinazoline-1,6(2H,5H)-dione 1H-[1,3]oxazino[3,4-a]indol-1-one derivatives broad range functional group tolerance moderate excellent yields. Furthermore, the synthetic utility was extended for various chemical transformations easily scaled up large-scale level.

Язык: Английский

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