Nickel-catalysed enantioselective alkene dicarbofunctionalization enabled by photochemical aliphatic C–H bond activation

Nature Catalysis, Год журнала: 2024, Номер 7(6), С. 655 - 665

Опубликована: Апрель 29, 2024

Abstract The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report three-component dicarbofunctionalization capitalizing on direct activation C( sp 3 )–H bonds through combination photocatalysed hydrogen atom transfer nickel catalysis. This protocol provides efficient for installing two vicinal carbon–carbon across alkenes atom-economic fashion, providing wide array high-value α-aryl/alkenyl carbonyls phosphonates, well 1,1-diarylalkanes ubiquitous alkane, ether alcohol feedstocks. method exhibits operational simplicity, broad substrate scope regioselectivity, chemoselectivity enantioselectivity. compatibility with bioactive motifs expedient synthesis pharmaceutically relevant highlight synthetic potential protocol.

Язык: Английский

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Divergent Access to Chiral C2- and C3-Alkylated Pyrrolidines by Catalyst-Tuned Regio- and Enantioselective C(sp³)–C(sp³) Coupling

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15456 - 15464

Опубликована: Июнь 12, 2023

Novel-substituted pyrrolidine derivatives are widely used in drugs and bioactive molecules. The efficient synthesis of these valuable skeletons, especially enantiopure derivatives, is still recognized as a key bottleneck to overcome chemical synthesis. Herein, we report highly catalyst-tuned regio- enantioselective hydroalkylation reaction for the divergent chiral C2- C3-alkylated pyrrolidines through desymmetrization readily available 3-pyrrolines. catalytic system consists CoBr2 with modified bisoxazoline (BOX) ligand, which can achieve asymmetric C(sp3)-C(sp3) coupling via distal stereocontrol, providing series high efficiency. Moreover, nickel allows synthesize C2-alkylated tandem alkene isomerization/hydroalkylation reaction. This method uses catalysts, BOX ligands, reagents, delivering enantioenriched 2-/3-alkyl substituted excellent enantioselectivity (up 97% ee). We also demonstrate compatibility this transformation complex substrates derived from molecules good efficiency, offers distinct entry more functionalized N-heterocycles.

Язык: Английский

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Dual Nickel/Photoredox‐Catalyzed Asymmetric Carbamoylation of Benzylic C(sp³)−H Bonds

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(12)

Опубликована: Янв. 12, 2024

Abstract Radical‐mediated Hydrogen Atom Abstraction of Csp 3 −H bonds has become a powerful tool for the asymmetric functionalization organic feedstocks. Here, we present an synthesis α ‐aryl amides via carbamoylation alkylarenes with isocyanates as electrophiles. The synergistic combination photoredox and chiral nickel‐catalyst, enables use readily available neutral reagents under mild reaction conditions provides straightforward access to pharmacologically relevant motifs in enantiomerically pure form.

Язык: Английский

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Visible-light induced direct C(sp³)–H functionalization: recent advances and future prospects

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5278 - 5305

Опубликована: Янв. 1, 2024

This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.

Язык: Английский

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Generation and Application of Aryl Radicals Under Photoinduced Conditions

Chemistry - A European Journal, Год журнала: 2024, Номер 30(31)

Опубликована: Март 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Язык: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Год журнала: 2024, Номер 124(17), С. 10192 - 10280

Опубликована: Авг. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Язык: Английский

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Enantiocovergent Cross-Coupling Reaction with 1,4-Dihydropyridine Derivatives via Photoinduced Nickel Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3278 - 3286

Опубликована: Фев. 15, 2024

Herein, we reported the enantioconvergent Csp3–Csp2 cross-coupling reaction with 1,4-dihydropyridine (DHP) derivatives via photoredox/nickel dual catalysis to access chiral products good yield and enantioselectivity. The operationally simple was carried out under mild conditions functional group tolerance. Due use of a stoichiometric equivalent aryl/alkenyl halides as coupling partners, sequential iterative synthesis could be achieved smoothly in one pot for position isomers stereoisomers. In proposed mechanism, kinetic experiments mechanistic studies indicated that radical generation, depended on excited photocatalyst DHP, rate-determining step.

Язык: Английский

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C(sp³)‐H Functionalization Using Chlorine Radicals

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(13), С. 2898 - 2918

Опубликована: Май 18, 2024

Abstract Converting any desired C−H bond to the intended C−Z in a given organic molecule could be final peak of functionalization methodology. Among three types bonds, ubiquitous C( sp 3 )−H has gained particular attention, especially last two decades. There are different ways transform bonds into bonds. The use chlorine radicals is one these methods with promising future. literature review shows that sources have been used for chlorine, including chloride ions (HCl or salts), coordinated chlorides (transition metal complexes), and (organochlorine compounds). However, HCl FeCl most attention among sources. major convert from radicals: 1) oxidation hydrogen salts, 2) photolysis chloride, 3) transition insertion C−Cl This summarizes published research papers on functionalization. Therefore, chlorination reactions which do not play direct role cleavage within scope this review.

Язык: Английский

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Ni/Photoredox-Catalyzed Enantioselective Acylation of α-Bromobenzoates with Aldehydes: A Formal Approach to Aldehyde-Aldehyde Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 19909 - 19918

Опубликована: Июнь 12, 2024

The catalytic cross-coupling of identical or similar functional groups is a cornerstone strategy for carbon-carbon bond formation, as exemplified by renowned methods, such olefin cross-metathesis, Kolbe electrolysis, and various cross-electrophile couplings. However, methodologies coupling aldehydes─fundamental building blocks in organic synthesis─remain underdeveloped. While the benzoin-type condensation, first reported 1832, offers reliable route aldehyde dimerization, chemo- enantioselective nonidentical yet aldehydes remains an unsolved challenge. Herein, we report unified platform enabling highly aldehydes. By leveraging nickel photoredox catalysis tandem with discrete activation strategies each aldehyde, this mechanistically distinct approach facilitates union aldehyde-derived α-oxy radical acyl radical, photocatalytically generated from aldehyde. This novel enables modular access to enantioenriched α-oxygenated ketones two minimally differentiated aliphatic substituents, feat not achievable existing chemocatalytic biocatalytic techniques. synthetic utility method demonstrated its application streamlined asymmetric synthesis medicinally relevant molecules. Additionally, mechanistic investigations rationalize versatility exploit new pathways addressing long-standing challenges.

Язык: Английский

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Direct stereoselective C(sp3)–H alkylation of saturated heterocycles using olefins

Nature Chemistry, Год журнала: 2025, Номер 17(3), С. 344 - 355

Опубликована: Фев. 28, 2025

Язык: Английский

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