γ-Amino Alcohols via Energy Transfer Enabled Brook Rearrangement

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10899 - 10907

Опубликована: Апрель 3, 2024

In the long-standing quest to synthesize fundamental building blocks with key functional group motifs, photochemistry in recent past has comprehensively established its attractiveness. Amino alcohols are not only functionally diverse but ubiquitous biologically active realm of compounds. We developed bench-stable bifunctional reagents that could then access sparsely reported γ-amino directly from feedstock alkenes through energy transfer (EnT) photocatalysis. A designed 1,3-linkage across is made possible by intervention a radical Brook rearrangement takes place downstream EnT-mediated homolysis our reagent(s). combination experimental mechanistic investigations and detailed computational studies (DFT) indicates chain propagated reaction pathway.

Язык: Английский

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Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1854 - 1941

Опубликована: Янв. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Язык: Английский

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Photocatalytic selective 1,4-oxyimination/diamination across C=C and N=N bonds to access structurally diverse N-N-N triazane derivatives

Green Synthesis and Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Авг. 1, 2024

A highly selective and atom-economical multi-component remote difunctionalization strategy has been successfully developed. This utilizes precise control over the radical properties of bifunctional precursors electronic traits olefins diazenes to achieve effective radical-mediated 1,4-oxyimination/diamination across C=C N=N bonds. By capitalizing on compatibility reactivity tuning, this approach enables synthesis complex triazine compounds with an N-N-N framework, providing a versatile tool for constructing diverse molecular structures. metal-free method is atom-efficient adaptable various substrates, demonstrating remarkable tolerance broad range functional groups.

Язык: Английский

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Efficient and regioselective C=S bond difunctionalization through a three-component radical relay strategy

Chinese Chemical Letters, Год журнала: 2024, Номер unknown, С. 110424 - 110424

Опубликована: Сен. 1, 2024

Язык: Английский

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Cyclic Bifunctional Reagents Enabling a Strain-Release-Driven Formal [3 + 2] Cycloaddition of 2H-Azirines by Cascade Energy Transfer

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

Опубликована: Апрель 10, 2025

The energy transfer (EnT)-catalyzed ring opening and further decarboxylation of isoxazole-5(4H)-ones enables the in situ generation strained 2H-azirines. Subsequent selective C(sp2)-C(sp3) bond cleavage azirine intermediate allows a formal [3 + 2] cycloaddition with wide range electrophiles, unlocking access to valuable pyrroline-type moieties. Mechanistic experiments combination density functional theory (DFT) calculations revealed unique nature EnT-cascade process for three-membered aza-cycle while providing insight into regio- diastereoselectivity annulation. This mild straightforward method ensures rapid construction highly substituted cyclic imines, which can be easily converted pyrrolidines, fused oxaziridines, biologically relevant β-amino acid precursors.

Язык: Английский

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Photoinduced EnT-Mediated Sulfonamidylimination of Alkenes and (Hetero)arenes with Iminophenylacetic Acids Oxime Esters

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Sulfonamidyl radicals are generated via photoinduced EnT and applied for the diamination of alkenes (hetero)arenes.

Язык: Английский

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Iron(II)‐Catalyzed 1,2‐Diamination of Styrenes Installing a Terminal NH2 Group Alongside Unprotected Amines

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 17, 2024

1,2-Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N-functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2-diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N-heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2-aminothiolation styrenes.

Язык: Английский

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Photocatalyzed Imino-Difluoromethylation of Alkenes with Bifunctional Oxime Esters

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13585 - 13594

Опубликована: Сен. 11, 2024

Herein, we report a simple and versatile difluoromethylene-imide reaction in which series of olefins can undergo difluoromethylenimine under photocatalytic conditions through an energy transfer (EnT) process. The has mild wide range applicability. We successfully synthesized 27 molecules containing difluoromethylene units, featuring easily accessible starting materials operational simplicity.

Язык: Английский

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Azocarboxamide-enabled enantioselective regiodivergent unsymmetrical 1,2-diaminations

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 26, 2024

Язык: Английский

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Iron(II)‐Catalyzed 1,2‐Diamination of Styrenes Installing a Terminal NH₂ Group Alongside Unprotected Amines

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Июль 17, 2024

Abstract 1,2‐Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N‐functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2‐diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N ‐heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2‐aminothiolation styrenes.

Язык: Английский

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