Light-empowered contra-thermodynamic stereochemical editing

Nature Reviews Chemistry, Год журнала: 2022, Номер 7(1), С. 35 - 50

Опубликована: Ноя. 16, 2022

Язык: Английский

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Biomimetic 1,2-amino migration via photoredox catalysis

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Synthetic organic chemists continually draw inspiration from biocatalytic processes to innovate synthetic methodologies beyond existing catalytic platforms. Within this context, although 1,2-amino migration represents a viable biochemical process, it remains underutilized within the chemistry community. Here we present biomimetic accomplished through synergistic combination of mechanism and photoredox catalysis. This platform enables modular synthesis γ-substituted β-amino acids by utilizing abundant α-amino-acid derivatives readily available molecules as coupling partners. mild method features excellent substrate functionality compatibility, affording diverse range (more than 80 examples) without need for laborious multistep synthesis. Mechanistic studies, supported both experimental observations theoretical analysis, indicate that involves radical addition α-vinyl-aldimine ester, 3-exo-trig cyclization subsequent rearrangement process. We anticipate transformation will serve versatile highly efficient construction unnatural acids. Enzyme-catalysed process is currently Building upon mechanism, photoredox-catalysed has been developed. By integrating conditions, approach library

Язык: Английский

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Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Авг. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Язык: Английский

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Energy- and atom-efficient chemical synthesis with endergonic photocatalysis

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(10), С. 745 - 755

Опубликована: Сен. 23, 2022

Язык: Английский

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Functional-group translocation of cyano groups by reversible C–H sampling

Nature, Год журнала: 2023, Номер 620(7976), С. 1007 - 1012

Опубликована: Июнь 26, 2023

Язык: Английский

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Ratcheting synthesis

Nature Reviews Chemistry, Год журнала: 2023, Номер 8(1), С. 8 - 29

Опубликована: Дек. 15, 2023

Язык: Английский

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Endergonic synthesis driven by chemical fuelling

Nature Synthesis, Год журнала: 2024, Номер 3(6), С. 707 - 714

Опубликована: Март 11, 2024

Abstract Spontaneous chemical reactions proceed energetically downhill to either a local or global minimum, limiting possible transformations those that are exergonic. Endergonic do not spontaneously and require an input of energy. Light has been used drive number deracemizations thermodynamically unfavourable bond-forming reactions, but is restricted substrates can absorb, directly indirectly, energy provided by photons. In contrast, anabolism involves uphill powered fuels. Here we report on the transduction from artificial fuel Diels–Alder reaction. Carboxylic acid catalysed carbodiimide-to-urea formation chemically orthogonal reaction diene dienophile, transiently brings functional groups into close proximity, causing otherwise prohibited cycloaddition in modest yield (15% after two fuelling cycles) with high levels regio- (>99%) stereoselectivity (92:8 exo : endo ). Kinetic asymmetry cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism (an information ratchet, depending synthetic protocol), reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand chemistry toolbox terms reactivity, complexity control.

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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Organic Synthesis Away from Equilibrium: Contrathermodynamic Transformations Enabled by Excited-State Electron Transfer

Accounts of Chemical Research, Год журнала: 2024, Номер 57(13), С. 1827 - 1838

Опубликована: Июнь 21, 2024

ConspectusChemists have long been inspired by biological photosynthesis, wherein a series of excited-state electron transfer (ET) events facilitate the conversion low energy starting materials such as H

Язык: Английский

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(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(39), С. 26766 - 26776

Опубликована: Сен. 20, 2024

The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- stereoselectivity challenges, typically yielding

Язык: Английский

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