Transition-metal-catalyzed C–H bond alkylation using olefins: recent advances and mechanistic aspects

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(17), P. 7358 - 7426

Published: Jan. 1, 2022

Transition metal catalysis has contributed immensely to C-C bond formation reactions over the last few decades, and alkylation is no exception. The superiority of such methodologies traditional evident from minimal reaction steps, shorter times, atom economy while also allowing control regio- stereo-selectivity. In particular, hydrocarbonation alkenes grabbed increased attention due its fundamental ability effectively selectively synthesise a wide range industrially pharmaceutically relevant moieties. This review attempts provide scientific viewpoint systematic analysis recent developments in transition-metal-catalyzed various C-H bonds using simple activated olefins. key features mechanistic studies involved these transformations are described briefly.

Language: Английский

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Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 26, 2023

Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation regioselectivity and complicated reaction patterns. Herein, we report straightforward Pd-catalyzed ring-opening hydrophosphinylation MCPs via highly selective C-C bond cleavage. This method allows for rapid efficient access wide range chiral allylic phosphine oxides in good yields high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed elucidate mechanism origin enantioselectivity.

Language: Английский

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Cobalt‐Catalyzed Regiodivergent Ring‐Opening Dihydroboration of Arylidenecyclopropanes to Access Skipped Diboronates

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 7, 2023

Ligand-controlled regiodivergent cobalt-catalyzed ring-opening dihydroboration of arylidenecyclopropanes is developed to access synthetically versatile skipped diboronates with catalysts generated in situ from Co(acac)2 and dpephos or xantphos. A variety reacted pinacolborane (HBpin) form the corresponding 1,3- 1,4-diboronates high isolated yields regioselectivity. Skipped diboronate products these reactions can undergo various transformations allow selective installation two different functional groups along alkyl chains. Mechanistic studies suggest that combine hydroboration homoallylic allylic boronate intermediates.

Language: Английский

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Room temperature photo-promoted iron-catalysed arene C–H alkenylation without Grignard reagents

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(3), P. 273 - 284

Published: Feb. 13, 2024

Language: Английский

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Three-Component Coupling of Arenes, Ethylene, and Alkynes Catalyzed by a Cationic Bis(phosphine) Cobalt Complex: Intercepting Metallacyclopentenes for C–H Functionalization

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(10), P. 4530 - 4540

Published: March 4, 2022

A cobalt-catalyzed intermolecular three-component coupling of arenes, ethylene, and alkynes was developed using the well-defined air-stable cationic bis(phosphine) cobalt(I) complex, [(dcype)Co(η6-C7H8)][BArF4] (dcype = 1,2-bis(dicyclohexylphosphino)ethane; BArF4 B[(3,5-(CF3)2)C6H3]4), as precatalyst. All three components were required for turnover formation ortho-homoallylated arene products. range directing groups including amide, ketone, 2-pyridyl substituents on promoted reaction. The method exhibited broad functional group tolerance allowing late-stage functionalization two drug molecules, fenofibrate haloperidol. series control reactions, deuterium labeling studies, resting state analysis, well synthesis substrate- product-bound η6-arene complexes supported a pathway involving C(sp2)–H activation from cobalt(III) metallacycle.

Language: Английский

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Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Advanced Science, Journal Year: 2024, Volume and Issue: 11(21)

Published: March 13, 2024

Abstract Chiral 1, n‐bis(boronate) plays a crucial role in organic synthesis and medicinal chemistry. However, their catalytic asymmetric has long posed challenge terms of operability accessibility from readily available substrates. The recent discovery the C═C bond formation through β‐C elimination methylenecyclopropanes (MCP) provided an exciting opportunity to enhance molecular complexity. In this study, catalyzed cascade hydroboration MCP is developed. By employing different ligands, various homoallylic boronate intermediate are obtained ring opening process. Subsequently, with HBpin or B 2 pin resulted enantioenriched chiral 1,3‐ 1,4‐bis(boronates) high yields, accompanied by excellent chemo‐ enantioselectivities. selective transformation these two distinct C─B bonds also demonstrated application potential synthesis.

Language: Английский

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Cyclometallated Iron(II) Alkoxides in Iron-Catalyzed C–H Activations by Weak O-Carbonyl Chelation

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(9), P. 4947 - 4960

Published: April 12, 2022

Iron catalysts represent an economically attractive tool for C–H activations because of their low costs and toxicities. Despite exponential increase interest in this area, detailed mechanistic understanding remains at a nascent stage. Herein, investigation the activation mechanism with [Fe(PMe3)4] unraveled unexpected iron(II) alkoxide intermediate that was fully characterized found to be more active catalyst phenone-assisted respect previously reported mer-iron hydride cyclometallated counterpart. Mechanistic studies by stoichiometric experimentation, reaction profiling through electron paramagnetic resonance (EPR) operando NMR spectroscopy, deuterium labeling, crystallographic analyses, density functional theory (DFT) calculations provided strong evidence oxidative addition pivalophenone low-valent iron toward formation transient fac-hydride complex, which very quickly rearranges complex. According DFT studies, it is proposed isolated highly reactive precatalyst, can easily access on-cycle thereby translating into efficient catalysis. These insights form basis further developments iron-catalyzed prospects stereoselective transformations.

Language: Английский

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Iron/Photosensitizer-Catalyzed Directed C–H Activation Triggered by the Formation of an Iron Metallacycle

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4552 - 4559

Published: March 21, 2023

C–H functionalization reactions catalyzed by iron, the most abundant transition metallic element in Earth's crust, are one of ideal synthetic methods. However, there a limited number strategies for iron-catalyzed directed activation when compared to other first-row metals. Here, we report iron/photosensitizer-catalyzed alkenylation amide derivatives via σ-CAM (σ-complex-assisted metathesis) promoted situ generation an iron metallacycle. Mechanistic experiments suggest that bond cleavage would proceed from metallacycle generated rather than oxidative addition low-valent species.

Language: Английский

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The fun of challenging something different from others

Journal of Synthetic Organic Chemistry Japan, Journal Year: 2025, Volume and Issue: 83(1), P. 63 - 67

Published: Jan. 1, 2025

Language: Английский

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Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6881 - 6894

Published: April 14, 2025

Language: Английский

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