Photochemical Alkylamination of Olefins through Reactivity-Based Sorting of Alkyl Radicals

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Alkyl radicals represent some of the most intriguing prospects in organic synthesis, showing diverse patterns reactivity for versatile transformations. In light this, methyl radical, addition to being a methylating agent, is also good proposition hydrogen atom transfer (HAT). Similarly, acetonitrile has dual facets its reactivity, acting as an amination reagent Ritter reaction while progenitor cyanomethyl through HAT. We hereby take advantage merging reactivities these radicals, allowing facile access amines various types from olefins when conjugated with photoredox amination.

Language: Английский

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Redox-Selective Macromolecular Electrolysis for Sequential Functionalization and Deconstruction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

This study demonstrates that selective macromolecular electrolysis can be achieved on copolymers containing redox-orthogonal targets by controlling the externally applied voltage. We designed macromolecules phthalimide (E1/2 = -1.8 V vs Ag/AgNO3) and tetrachlorophthalimide -1.3 (meth)acrylates have significantly different reduction potentials such they are separately redox-addressable. The polymer-centered radicals generated decarboxylation either undergo (1) hydrogen atom transfer to form olefinic repeat units or (2) β-scission deconstruct polymer backbone. Our results reveal electrochemical control over postpolymerization modifications, which enables sequential transformations tune glass transition temperature of electrochemically a range -54 125 °C. method was also shown maintain its selectivity in blend provided access (poly(styrene-co-propylene-co-ethylene)) would challenging prepare other ways. These demonstrate potential for material functionalization degradation. approach expands toolbox modification targeted degradation with applications information processing, spatiotemporal patterning, producing materials complex architectures driven external stimuli.

Language: Английский

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Straightforward Superbase-Mediated Reductive O-Phosphorylation of Aromatic and Heteroaromatic Ketones with Red Phosphorus in the Superbase Suspension KOH/DMSO(H2O)

Molecules, Journal Year: 2025, Volume and Issue: 30(6), P. 1367 - 1367

Published: March 18, 2025

It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in superbase suspension KOH/DMSO(H2O) at 85 °C 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates were earlier inaccessible a yield up 45%. The ESR data demonstrate unlike previously published phosphorylation elemental phosphorus, this new reaction proceeds via single electron transfer from polyphospide anions diaryl(hetaryl)ketones. This is example C-O-P bond generation during strongly basic media, which usually provides C-P formation.

Language: Английский

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Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 5, 2025

Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration asymmetric catalysis. While the dual-catalytic approach led to successful examples of control stereogenic centers, axes remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, symmetric substrate, 2-arylresorcinol, desymmetrized aid chiral phosphoric acid Using approach, center axis were successfully controlled provide natural-product-driven compound. The origins enantioselectivity diastereoselectivity investigated density functional theory study four possible enantiodetermining transition states. Consequently, first total syntheses ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A B accomplished concisely. This provides not only novel methodology strategy synthesize alkaloids but also direction advance catalytic research synthesis studies.

Language: Английский

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Organic N-hydroxyphthalimide catalyzes the selective aerobic oxidation of hydrocarbons promoted by the nonionic surfactants through hydrogen bonding effect

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 580, P. 115110 - 115110

Published: April 16, 2025

Language: Английский

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Red-shifted photoredox generation and trapping of alkyl radicals towards bioorthogonality

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We report two potentially biocompatible photoredox systems for the activation and coupling of redox-active esters using low-energy light BnNAH as reductant.

Language: Английский

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Acyl radicals generated from aldehydes with NHPI as electrocatalyst: aldehydes and alcohols as carbon-centered radical precursors

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4842 - 4848

Published: Jan. 1, 2024

We describe how N -hydroxyphthalimide (NHPI) promotes hydrogen atom transfer from aldehydes under electrochemical conditions. NHPI plays a multifunctional role, enabling the consideration of or alcohols as sp 3 -carbon centered radicals.

Language: Английский

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Light‐Mediated Radical Addition to Azomethine Compounds: Novel Reactivity and Activation Modes

The Chemical Record, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 17, 2024

Abstract Azomethines is a class of compounds, which have traditionally served as electrophilic substrates, but their reactions with radicals long been limited. Photocatalysis provided ample opportunities for promoting these reactions, wide variety reagents serving precursors radicals. Besides regular addition mode at the azomethine fragment, oxidative pathway, in C=N bond remains product, has become possible by proper selection redox catalyst. This review summarizes new developments this rapidly developing field over past five years. New concepts on activation towards radical attack are discussed.

Language: Английский

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