Radical philicity and its role in selective organic transformations

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(7), С. 486 - 499

Опубликована: Июнь 22, 2021

Язык: Английский

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Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles

Chemical Society Reviews, Год журнала: 2021, Номер 50(6), С. 4162 - 4184

Опубликована: Янв. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Язык: Английский

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Photoinduced gold-catalyzed divergent dechloroalkylation of gem-dichloroalkanes

Nature Catalysis, Год журнала: 2022, Номер 5(12), С. 1098 - 1109

Опубликована: Дек. 15, 2022

Язык: Английский

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General method for iron-catalyzed multicomponent radical cascades–cross-couplings

Science, Год журнала: 2021, Номер 374(6566), С. 432 - 439

Опубликована: Окт. 22, 2021

Iron links a trio holds particular appeal as catalytic metal—it is safe and abundant, well mainstay of enzymatic reactivity. Nonetheless, in synthetic construction carbon-carbon bonds, modern chemists have largely had to rely on rarer metals such palladium. Liu et al . now report that coordination iron by bulky chelating phosphine ligand enables efficient mutual coupling three different reactants—an alkyl halide, an aryl Grignard, olefin—to form two bonds (see the Perspective Lefèvre). A combination Mössbauer spectroscopy, crystallography, computational simulations illuminates mechanism. —JSY

Язык: Английский

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Advances in transition metal-free deborylative transformations of gem-diborylalkanes

Chemical Communications, Год журнала: 2021, Номер 57(36), С. 4346 - 4353

Опубликована: Янв. 1, 2021

This article highlights recent advances on the base-promoted deborylative carbon–carbon and carbon–boron bond-forming reactions using gem-diborylalkanes as sources of α-borylcabanions.

Язык: Английский

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The Impact of Boron Hybridisation on Photocatalytic Processes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)

Опубликована: Июнь 24, 2022

Recently the fruitful merger of organoboron chemistry and photocatalysis has come to forefront organic synthesis, resulting in development new technologies access complex (non)borylated frameworks. Central success this combination is control boron hybridisation. Contingent on photoactivation mode, as its neutral planar form or tetrahedral boronate can be used regulate reactivity. This Minireview highlights current state art photocatalytic processes utilising compounds, paying particular attention role hybridisation for target transformation.

Язык: Английский

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Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Март 6, 2024

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α-halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross-coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron-containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Язык: Английский

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Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 15850 - 15859

Опубликована: Май 28, 2024

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored comparison to transition-metal-based technologies, yet desirable when considering controlled exploration chemical space. With current drive discover next-generation therapeutics, reaction design enables strategic incorporation an sp3 carbon center, containing multiple synthetic handles for subsequent space would be highly enabling. Here, we describe photoactivation ambiphilic C1 units generate α-bimetalloid radicals using only Lewis base and light source directly activate C–I bond. Interception these transient with various SOMOphiles rapid synthesis organic scaffolds (B, Si, Ge) orthogonal activation. In-depth theoretical mechanistic studies reveal prominent role 2,6-lutidine forming photoactive charge transfer complex stabilizing situ generated iodine radicals, as well influential boron p-orbital activation/weakening This simple efficient methodology enabled expedient access functionalized 3D frameworks can further derivatized available technologies C–B C–Si

Язык: Английский

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PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Язык: Английский

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1,n-Bisborylalkanes via Radical Boron Migration

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(20), С. 9119 - 9123

Опубликована: Май 4, 2020

A systematic study of radical boron migration in diboronate complexes to form synthetically valuable 1,

Язык: Английский

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