Regiodivergent Hydroamidation of Alkenes via Cobalt-Hydride Catalysis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Regiodivergent hydroamin(d)ation of alkenes presents a valuable strategy for the synthesis diverse amines or amides from common set starting materials, yet achieving controlled regioselectivity remains significant challenge. In this work, we present cobalt-catalyzed regiodivergent hydroamidation alkenes, enabling enantioselective ipso- and migratory heterocyclic alkenes. The ability to finely tune various reaction parameters allows seamless switch in regioselectivity. Notably, selectivity are governed by choice cobalt catalyst anions. Mechanistic studies reveal neutral Co-H species mediating ipso-hydroamidation cationic intermediate promoting hydroamidation. This protocol exhibits broad substrate scope, high functional group tolerance, provides an efficient pathway synthetizing structurally amides.

Язык: Английский

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Photo-induced dehalogenative deuteration and elimination of alkyl halides enabled by phosphine-mediated halogen-atom transfer

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A photocatalytic phosphine-mediated strategy for the dehalogenative deuteration of unactivated alkyl halides is herein reported.

Язык: Английский

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Photoredox and Cobalt-Catalyzed Markovnikov-Selective Radical Hydroamination of Unactivated Alkenes with Anilines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 26, 2025

The intermolecular hydroamination of unactivated alkenes with simple amines continues to be an attractive and challenging undertaking in organic synthesis. current state-of-the-art strategies for photocatalyzed usually commence the formation a C–N bond, thereby delivering exclusively anti-Markovnikov products. We herein reported facile mild Markovnikov anilines through photoredox cobalt-catalyzed hydrogen atom transfer followed by radical-polar crossover nucleophilic amination process. reaction features wide substrate scope, good functional group tolerance, excellent yields. Application this late-stage functionalization relatively complex natural products bioactive molecules further increases utility developed methodology.

Язык: Английский

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Photocatalytic Phosphine-Mediated Deoxygenative [3 + 2] Cycloaddition of α,β-Unsaturated Carbonyls and Alkenes

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

Tertiary phosphine is a powerful nucleophile that enables numerous synthetically important reactions. However, the exclusive reliance on two-electron pathway has restricted development of chemistry. We report here visible light photocatalytic phosphine-mediated deoxygenative [3 + 2] cycloaddition α,β-unsaturated carbonyls and activated alkenes, providing facile access to polysubstituted cyclopentenes from readily accessible starting materials in promising yields with good substrate scope. Mechanistic investigations corroborate transient involvement radical cation consequent α-addition (α electron-withdrawing groups) C-C double bonds due inherent electrophilicity cation, as opposed traditional nucleophilic β-addition phosphine. The ensuing single electron transfer reduction, Michael addition, 1,4-proton cascade furnish phosphorus ylide, which undergoes an intramolecular Wittig reaction finish construction cyclopentenes. This work demonstrates tertiary can serve convenient reagent for carbonyl deoxygenation act traceless directing group controllable cross-coupling two distinct new avenues expand frontiers chemistry synthetic

Язык: Английский

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Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins

Advanced Science, Год журнала: 2024, Номер 12(2)

Опубликована: Ноя. 18, 2024

Abstract Allylic amide moieties are commonly encountered in natural products and privileged structures pharmaceuticals agrochemicals. Moreover, because allylic can be to converted into an array of high‐value motifs, they have been widely employed organic synthesis. However, the development catalytic systems for intermolecular amidation olefins, particularly branched α ‐olefins, has proven challenging. Here, a biomimetic, synergistic method is reported that combines photoredox, cobalt, Brønsted base catalysis synthesis substituted amides from ‐olefins simple imides without using oxidants. This low‐cost, operationally features broad substrate scope excellent functional group compatibility. it successfully used functionalization several structurally complex molecules demonstrating method's potential utility medicinal chemistry applications. Mechanistic studies revealed C( sp 3 )─N bond formation mediated by nitrogen‐centered radical intermediate, which generated via sequence involving deprotonation single‐electron oxidation.

Язык: Английский

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Enantioselective Synthesis of Aminals Via Nickel-Catalyzed Hydroamination of 2-Azadienes with Indoles and N-Heterocycles

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(45), С. 30947 - 30957

Опубликована: Окт. 30, 2024

New methods for the enantioselective synthesis of N-alkylated indoles and their derivatives are great interest because pivotal structural elements in biologically active molecules natural products. They also versatile intermediates organic synthesis. Among well-established asymmetric hydroamination methods, with indole-based substrates is a formidable challenge. This observation likely due to reduced nucleophilicity indole nitrogen. Herein, unique nickel-catalyzed enantio- branched-selective 2-azadienes structurally related N-heterocycles reported generation enantioenriched

Язык: Английский

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