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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Photoredox-Catalyzed Alkene Acylesterification with Acyloxime Esters via C–C and Tertiary C–O Bond Formation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

We describe an efficient acyl esterification method for alkenes utilizing acyloxime esters as bifunctional reagents featuring radical acylation and congested C–O bond formation. This approach is characterized by mild photoredox conditions, high step atom economy, a broad substrate scope, excellent regioselectivity. A variety of valuable α-acyl hindered alcohol esters, including those obtained via gram-scale synthesis late-stage functionalization pharmaceutical molecules, were presented, demonstrating its synthetic potential practicability.

Язык: Английский

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Photosensitized Imino-Thiocyanation of Alkenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

A metal-free photosensitized 1,2-imino-thiocyanation of olefins has been established by using the easily accessible bifunctional reagent S-cyano-N-(diphenylmethylene) thiohydroxylamine. wide range were successfully transformed into corresponding β-iminothiocyanates in moderate to high yields. This protocol stands out for its nature, broad substrate compatibility, and atom step economy, providing an effective strategy assembling β-amino thiocyanate-containing scaffolds.

Язык: Английский

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Visible-Light-Induced Decarboxylative Aminosulfonylation of (Hetero)aryl Carboxylic Oxime Esters

Organic Letters, Год журнала: 2024, Номер 26(3), С. 713 - 718

Опубликована: Янв. 12, 2024

Sulfonamides are important structures in pharmaceuticals, agrochemicals, and organocatalysts, yet the rapid benign synthesis of these compounds is still a great challenge. Herein we report photoinduced method for synthesizing sulfonamides from (hetero)aryl carboxylic acid oxime esters. This reaction proceeds via one-pot cascade radical–radical cross-coupling by energy-transfer-mediated photocatalysis. A wide substrate scope including substrates late-stage modification pharmaceutical molecular entities reveal its generality.

Язык: Английский

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Metal-free photosensitized aminosulfonylation of alkenes: a practical approach to β-amido sulfones

Green Chemistry, Год журнала: 2023, Номер 25(10), С. 3857 - 3863

Опубликована: Янв. 1, 2023

A general and environmentally friendly organic photo-induced strategy was developed for the synthesis of diverse alkyl-substituted β-amino sulfone derivatives, including primary, secondary, tertiary products.

Язык: Английский

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A radical Smiles rearrangement difunctionalization of activated alkenes via desulfonylation and insertion of sulfur dioxide relay strategy

Green Chemistry, Год журнала: 2024, Номер 26(11), С. 6774 - 6778

Опубликована: Янв. 1, 2024

A novel and attractive photochemical difunctionalization of N -tosyl acrylamide for constructing alkylsulfonylated oxindoles amides with excellent substrate adaptability via a radical Smiles rearrangement strategy is described.

Язык: Английский

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Photosensitized 1,2-Difunctionalization of Alkenes to Access β-Amino Sulfonamides

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2108 - 2113

Опубликована: Март 5, 2024

A metal-free photosensitized 1,2-imino-sulfamoylation of olefins by employing a tailor-made sulfamoyl carbamate as the difunctionalization reagent has been established. This protocol exhibits versatility across broad substrate scope, including aryl and aliphatic alkenes, leading to synthesis diverse β-imino sulfonamides in moderate good yields. method is characterized its reaction system, mild conditions, excellent regioselectivity, high atom economy, serving promising platform for preparation β-amino sulfonamide-containing molecules, particularly context drug discovery.

Язык: Английский

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Photo-induced imino functionalizations of alkenes via intermolecular charge transfer

Chemical Science, Год журнала: 2023, Номер 14(40), С. 11170 - 11179

Опубликована: Янв. 1, 2023

A catalyst-free photosensitized strategy has been developed for regioselective imino functionalizations of alkenes via the formation an EDA complex. This photo-induced protocol facilitates construction structurally diverse β-imino sulfones and vinyl in moderate to high yields. Mechanistic studies reveal that reaction is initiated with intermolecular charge transfer between oximes sulfinates, followed by fragmentation generate a persistent iminyl radical transient sulfonyl radical. also features excellent regioselectivity, broad functional group tolerance mild conditions. The late stage functionalization natural product derived compounds total synthesis some bioactive molecules have demonstrated highlight utility this protocol. Meanwhile, compatibility different donors proved generality strategy.

Язык: Английский

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Visible-Light-Induced Synthesis of Alkylsulfonated Isoquinolinones from 2-Aryl Indoles/Benzimidazoles through Insertion of Sulfur Dioxide

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 9293 - 9305

Опубликована: Июнь 7, 2023

A visible-light-induced three-component reaction of 2-aryl indoles/benzimidazoles, Hantzsch esters, and sodium pyrosulfite through a radical cascade cyclization process with the insertion sulfur dioxide is described. It provides novel powerful way for synthesis alkylsulfonated isoquinolinones. esters Na2S2O5 are employed as alkyl precursors SO2 surrogate, respectively. This transformation exhibits good functional group tolerance substrate applicability under mild conditions.

Язык: Английский

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Carbamoylarylation of Alkenes with N-Aryl Oxamic Acids Involving 1,4-Aryl Migration Via C(aryl)–N Bond Cleavage

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5972 - 5977

Опубликована: Апрель 4, 2024

We report carbamoylarylation of alkenes using N-aryl oxamic acid derivatives under visible-light irradiation. Reactions with carbamoyl radicals generated to afford Giese-type products or 3,4-dihydroquinolin-2(1H)-ones via ortho-radical addition an aryl amide moiety have been previously reported. However, this study reveals that the introduction a removable bulky group onto nitrogen atom acids facilitates radical alkenes, resulting in 1,4-aryl migration C(aryl)–N bond cleavage, thus affording arylpropanamides. Various such as acrylic and styrene derivatives, are successfully applied synthesis variety arylpropanamide including 1,4-dicarbonyl amides, forming two C–C bonds.

Язык: Английский

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