Organophotoredox Pd‐Catalyzed C–H Arylation at Room Temperature using Diaryliodonium Salts DOI Open Access

Christopher Bennett,

Nicholas McDonald, Amin A. Siddiqui

и другие.

ChemPhotoChem, Год журнала: 2024, Номер unknown

Опубликована: Окт. 24, 2024

Abstract Direct functionalization of C−H bonds is the most expeditious strategy to build complexity into organic molecules. Unfortunately, Pd‐catalyzed arylation strategies require high temperatures and/or stoichiometric oxidants. The discovery metallaphotoredox in 2011 forged a new approach achieve metal catalyzed at room temperature. Since this discovery, reports still use explosive diazonium salts as aryl radical precursors. Alternatively, single report uses bench‐stable diaryliodonium salts, albeit with an Ir‐based photocatalyst. In study, we develop organophotoredox manifold that enables numerous N ‐aryl amide substrates. results present are expected revitalize temperature arylations wide‐ranging classes bonds.

Язык: Английский

Stereospecific Assembly of Trisubstituted Alkenes via Photoinduced Nitrogen‐Centered Radical‐Triggered C—C Bond Cleavage/Functionalization of Oxime Esters DOI

Yu Bao,

Zhi‐Jie Song,

Jin‐Long Dai

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(12), С. 1399 - 1406

Опубликована: Фев. 29, 2024

Comprehensive Summary A general and convenient photoredox‐catalyzed acylation alkylcyanation of MBH acetates has been established, enabling the assembly C(sp 2 )–C(sp 3 ) bond by a nitrogen‐centered radical strategy for synthesis trisubstituted alkenes in moderate to excellent chemical yields (48 examples total). The reaction with acyl (indanone) oxime esters afforded containing 1,4‐dicarbonyl groups. Interestingly, use Eosin Y as photocatalyst catalytic system resulted formation distal cyano group‐anchored via deconstructive functionalization cycloketone esters. Notably, these resulting compounds could be applied late‐stage transformations, providing important methods dihydropyridazin‐3(2 H )‐one.

Язык: Английский

Процитировано

9

(Indol-3-yl)(DMIX)Iodonium Salts: Novel Electrophilic Indole Reagents DOI
Dmitry I. Bugaenko,

Nikolai A. Malashchenko,

Sergei O. Kopytov

и другие.

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3189 - 3194

Опубликована: Апрель 8, 2024

A new umpolung approach to the C3–H functionalization of indoles with diverse nucleophiles based on intermediate formation I(III) reagents is described. The 3,5-dimethylisoxazol-4-yl auxiliary allows for selective indole transfer under catalyst-free conditions, which was impossible using previously reported reagents. Combining mildness transition-metal-free conditions and high reactivity hypervalent iodine reagents, this protocol tolerates various functional groups provides access that are difficult prepare conventionally.

Язык: Английский

Процитировано

9

Photoinduced Alkylsulfonylation and Cyanoalkylsulfonylation of Morita–Baylis–Hillman Adducts via Multicomponent Insertion of Sulfur Dioxide DOI

Song Zhi-jie,

Yu Bao,

Yun-Jia Sun

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 4877 - 4887

Опубликована: Март 8, 2024

General and convenient visible-light-promoted alkylsulfonylation cyanoalkylsulfonylation of MBH adducts have been developed through the multicomponent insertion sulfur dioxide, enabling assembly two C–S bonds to generate structurally diverse allylic alkylsulfones (43 examples in total). The reaction with potassium alkyltrifluoroborates 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct afforded sulfones generally good yields. Notably, addition N,N,N′,N′-tetramethylethylenediamine as a base into photocatalytic system led yielding an alkyl sulfonyl unit cyano group-anchored trisubstituted alkenes by utilizing cycloketone oxime esters C-radical precursors. Both these reactions constructed bonds, all desired products were obtained moderate excellent yields complete stereospecificity.

Язык: Английский

Процитировано

6

Organophotocatalytic Carbamoylation of Morita‐Baylis‐Hillman Carbonates DOI
Lucas Marchini,

Jeimy A. C. Vélez,

Elias André

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(9), С. 2063 - 2071

Опубликована: Фев. 29, 2024

Abstract Herein, we demonstrate that carbamoyl radicals generated through an organophotocatalytic protocol from 4‐carbamoyl‐dihydropyridines (carbamoyl‐DHPs) can be incorporated into Morita‐Baylis‐Hillman (MBH) carbonates, affording a range of polyfunctionalized scaffolds with yields ranging 63–98%. Reaction monitoring experiments, scale‐up, reuse the organophotocatalyst, and hydrogenation succinamic ester's alkene moiety was also conducted, in order to showcase mechanistic features robustness this photochemical protocol.

Язык: Английский

Процитировано

3

Arylation of Diethyl Acetamidomalonate with Diaryliodonium Salts En Route to α-Arylglycines DOI
Dmitry I. Bugaenko,

Olga A. Tikhanova,

Valeriy V. Andreychev

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 9923 - 9928

Опубликована: Июль 1, 2024

Diethyl acetamidomalonate (DEAM) has been widely used for the synthesis of α-amino acids via C-alkylation under basic conditions followed by hydrolysis/decarboxylation. In contrast, C-arylation this reagent remains undeveloped. Herein, we report a novel strategy racemic α-arylglycines based on selective arylation DEAM with diaryliodonium salts mild, transition metal-free conditions. The reaction features good functional group tolerance and easy scalability is applicable to chemoselective C-H-modification arenes including approved drugs, thus enabling straightforward approach complex that would be challenging make otherwise.

Язык: Английский

Процитировано

3

Synthesis of Diaryl Ethers via Hypervalent Iodine-Mediated C–H Functionalization DOI

Chenghu Hu,

Qi Jia,

Wenjing Bao

и другие.

Organic Letters, Год журнала: 2024, Номер 26(37), С. 7864 - 7868

Опубликована: Сен. 9, 2024

A hypervalent iodine-reagent-based C-H functionalization strategy was utilized to synthesize diaryl ethers. This method directly transforms various arenes into their corresponding diaryliodonium salts, followed by a C-O coupling reaction produce structurally diverse The efficacy of this approach in the late-stage structural modifications complex molecules demonstrated.

Язык: Английский

Процитировано

3

β-Thioamide Sulfone Enabled Copper-Catalyzed Ring-Opening/Sulfonylation of Cyclopropenes: Access to Alkyl Aryl Sulfones DOI

Arshad Ali,

C.‐S. CHUNG, Jingru Wang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

Sulfone motifs play important roles in bioactive compounds and functional materials. The development of efficient methodologies for constructing sulfonyl-containing has thus attracted considerable attention. Here, we introduce a protocol the preparation alkyl aryl sulfones under mild conditions. This employs β-thioamide sulfone as novel motif donor. It forms sulfinates situ basic conditions, which then undergo cross-coupling with intermediates that were generated from ligand-free copper-catalyzed cyclopropenes (CPEs) ring opening.

Язык: Английский

Процитировано

0

Sustainable, precious-metal-free C–N cross coupling through photocatalysis DOI

Mohammad Hassam,

Samuelu Mamidipalli,

Akhila Ailaveni

и другие.

New Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Photoredox catalysis has evolved as a sustainable method of constructing C–N bonds.

Язык: Английский

Процитировано

0

Palladium-Catalyzed Decarboxylative Allylic Sulfonylation of Vinyloxazolidine-2,4-diones: Synthesis of γ-Sulfonyl-α,β-unsaturated Amides DOI
Wei‐Cheng Yuan, Xiaohui Fu, Yanping Zhang

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

A palladium-catalyzed decarboxylative allylic sulfonylation reaction of vinyloxazolidine-2,4-diones with inexpensive and readily available sodium sulfinates as reagents has been developed. Under the catalysis Pd(PPh3)4, a wide range γ-sulfonyl-α,β-unsaturated amides can be synthesized in good to excellent yields. The developed protocol is characterized by exclusive regioselectivity, mild conditions, broad substrate scope, functional group tolerance, suitable for gram-scale synthesis.

Язык: Английский

Процитировано

0

Photocatalytic 1,3-Difluoroalkylcarboxylation of Alkenes by Triple Kinetic-Controlled Radical Self-Ordering DOI Creative Commons

Hong Fu,

Zuo-Shuai Wang,

Sijia Li

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A transition-metal-free protocol for the unsymmetrical radical 1,3-difunctionalization of alkenes has been established first time in form 1,3-difluoroalkylcarboxylation by a photocatalytic three-component reaction allyl formates, trifluoroacetanilides, and cesium formate. This employs formate as carboxylating reagent trifluoroacetanilide difluoroalkylating via C-F bond activation. As result, series previously inaccessible difluorinated adipic acid derivatives can be easily efficient prepared. Mechanism studies reveal that triple kinetic-controlled self-ordering is key to this unique reaction. sorting involves fast initiation CO2 anion its chemoselective addition reduction, followed slow generation fluoroalkyl chemo-/regioselective addition. Notably, strategy also suitable cyclic through diastereoselectively constructing two or three consecutive stereocenters.

Язык: Английский

Процитировано

0