Photoinduced Asymmetric Alkene Aminohetarylation with Chiral Sulfoximine Reagents DOI Open Access
Zhu Cao,

Sun Yu-qian,

Yasu Chen

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(47)

Опубликована: Авг. 15, 2024

Abstract Given the pivotal role of β ‐(het)arylethylamine moiety in bioactive molecules, direct amino(het)arylation alkenes occupies a privileged position construction (het)arylethylamine derivatives. Herein we devise chiral sulfoximines as novel bifunctional reagents which exhibit remarkable efficiency challenging asymmetric alkene aminohetarylation reaction, particularly terms reactivity and stereo‐control. The can be conveniently accessed gram scale, efficiently generate N ‐centered radicals under mild photochemical conditions. transformation proceeds through enantioselective 1,4‐hetaryl migration, ensuring precise chirality transfer from sulfur‐ to carbon‐centers, rendering wide applicability both aromatic aliphatic alkenes. Furthermore, method is straightforward operate does not require transition metals or photosensitizers, making it an attractive practical option.

Язык: Английский

Electrochemical Difunctionalization of Alkenes DOI

Jing‐Hao Qin,

Jin‐Heng Li,

Ning Nan

и другие.

Synthesis, Год журнала: 2023, Номер 55(18), С. 2843 - 2859

Опубликована: Фев. 15, 2023

Abstract The electrochemical alkene difunctionalization reaction has become a powerful and sustainable tool for the efficient construction of vicinal difunctionalized structures in organic synthesis. Since only electrons are used as redox agents, avoids need additional catalysts, metal or chemical oxidants does not generate waste. Herein we summarize latest contributions alkenes over last 3–4 years. We discuss detail features, scope, limitations, mechanistic rationalizations three categories methods: (1) terminated by nucleophiles, (2) radicals, (3) functionality migration. 1 Introduction 2 Electrochemical Alkene Difunctionalization Terminated Nucleophiles 2.1 Sulfonylative Alkenes 2.2 Sulfurizative/Sulfoxidative 2.3 Azidotetrazolation 2.4 Trifluoromethylative 2.5 Diarylation 3 Radicals 3.1 Direct Radical-Coupling-Enabled 3.2 Metal-Mediated Radical Transfer Coupling Enabled 3.3 Metalloid-Mediated 4 Functionality Migration 5 Summary Outlook

Язык: Английский

Процитировано

23

Photocatalytic Cyclization Cascades by Radical Relay toward Pyrrolo[1,2-a]indoles: Synthesis, Mechanism, and Application DOI

Chen He,

Qi Wang,

Xiaoyang Zhou

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 3509 - 3524

Опубликована: Фев. 16, 2024

A photocatalytic annulation cascade of unactivated N-alkene-linked indoles with Langlois' reagent by a radical relay is developed at room temperature under blue LED irradiation. The reaction afforded series tri/difluoromethylated pyrrolo[1,2-a]indoles in moderate to good yields. DFT study suggests that the ascribed rhodamine 6G-induced cyclization involving vinyl addition-radical and hydrogen-atom-abstraction (HAA) processes, interestingly, are applied as fluorescent dyes into fluorescence spectrum live-cell imaging. This paper represents an initial example on cascades HAA process.

Язык: Английский

Процитировано

9

Regioselective electrochemical cascade C–H sulfonylation–bromination of indolizines to access difunctionalized indolizines DOI
Wenxuan Jiang, Xiang Liu, Chuanying Zhu

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(8), С. 2306 - 2312

Опубликована: Янв. 1, 2024

Regioselective electrochemical C–H sulfonylation–bromination between indolizines, sodium sulfinates, and KBr has been established in an undivided cell, which serves as both the brominating agent electrolyte.

Язык: Английский

Процитировано

8

Recent advances in the application of Langlois’ reagent in olefin difunctionalization DOI
Jiabin Shen, Lin Li, Jun Xu

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 21(10), С. 2046 - 2058

Опубликована: Ноя. 18, 2022

This review describes several key activation methods for Langlois' reagent in the difunctionalization of alkenes and could stimulate interest readers promoting wider development application reagent.

Язык: Английский

Процитировано

27

Photoinduced difunctionalizations of unactivated olefins enabled by ligand-to-iron charge transfer and functional group migration strategies DOI

Mengqi Luo,

Shibo Zhu,

Jiawen Yin

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 4748 - 4756

Опубликована: Янв. 1, 2024

Difunctionalizations of unactivated olefins with fluoroalkyl carboxylic acids or aldehydes via a radical-mediated functional group migration strategy are herein reported.

Язык: Английский

Процитировано

6

Photoinduced Asymmetric Alkene Aminohetarylation with Chiral Sulfoximine Reagents DOI
Zhu Cao,

Sun Yu-qian,

Yasu Chen

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(47)

Опубликована: Авг. 15, 2024

Abstract Given the pivotal role of β ‐(het)arylethylamine moiety in bioactive molecules, direct amino(het)arylation alkenes occupies a privileged position construction (het)arylethylamine derivatives. Herein we devise chiral sulfoximines as novel bifunctional reagents which exhibit remarkable efficiency challenging asymmetric alkene aminohetarylation reaction, particularly terms reactivity and stereo‐control. The can be conveniently accessed gram scale, efficiently generate N ‐centered radicals under mild photochemical conditions. transformation proceeds through enantioselective 1,4‐hetaryl migration, ensuring precise chirality transfer from sulfur‐ to carbon‐centers, rendering wide applicability both aromatic aliphatic alkenes. Furthermore, method is straightforward operate does not require transition metals or photosensitizers, making it an attractive practical option.

Язык: Английский

Процитировано

5

Electrosynthesis of β‐Acyloxy‐γ‐Selenyl Amines via Migratory Oxyselenation of N‐Acyl Allylamines DOI
Kejun Lin,

Jianyong Lan,

Tingshun Zhu

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(20), С. 3466 - 3471

Опубликована: Авг. 24, 2022

Abstract A metal‐free and external‐oxidant‐free electrosynthesis of β‐acyloxy‐γ‐selenyl amines was developed. The cascade reaction is triggered by anodic oxidative generation electrophilic selenium cation, followed addition to the unactivated alkene, successive water promoted intramolecular acyl migration. reactions gave products in up 98% yield with controllable regio‐ diastereoselectivities. Different chemoselectivity towards cyclization also viable N ‐Boc N‐ Cbz substrates. Both batch chemistry flow were available for scale‐up synthesis 91% yield. magnified image

Язык: Английский

Процитировано

17

Merging Fluorine Incorporation and Functional Group Migration DOI
Zhigang Ma, Xinxin Wu, Chen Zhu

и другие.

The Chemical Record, Год журнала: 2022, Номер 23(9)

Опубликована: Ноя. 11, 2022

Abstract Fluorine incorporation by concomitant fluoroalkyl radical addition to alkene or alkyne and functional group migration (FGM) represents an ingenious robust strategy for the synthesis of structurally diverse fluorinated compounds. This account gives overview related studies in our group, which three main reaction modes are discussed: 1) fluoroalkylative difunctionalization unactivated alkenes via intramolecular FGM; 2) docking‐migration process using fluoroalkyl‐containing bifunctional reagents; 3) into C(sp 3 )−H bond consecutive hydrogen atom transfer (HAT) FGM. Relying on these methods, a variety trifluoromethylation di‐/mono‐fluoroalkylation reactions along with cyano, heteroaryl, oximino, formyl, alkynyl, alkenyl groups have been accomplished under mild conditions.

Язык: Английский

Процитировано

17

Electrochemically Promoted Three-Component Reaction to N-Sulfonyl Amidines DOI
Zhang Zhang, Xiu‐Jin Meng, Fei‐Hu Cui

и другие.

Organic Letters, Год журнала: 2023, Номер 26(1), С. 193 - 197

Опубликована: Дек. 26, 2023

In this study, a multicomponent reaction via the Mannich intermediate was developed using methanol, secondary amine, and sulfonamide as starting materials. This method uses methanol green C1 source. The substrate scope is wide, yield good. mechanistic study shows that generates formaldehyde under electrochemical conditions, sulfonyl amidine nucleophile reacts with Schiff base intermediates to form N-sulfonyl in single step.

Язык: Английский

Процитировано

11

Electrochemical Synthesis of Aryl Chlorides Using HCl as the Chlorine Source DOI
Tao Shen,

Yuanbo Xu,

Chengjun Jiang

и другие.

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(8), С. 3289 - 3297

Опубликована: Фев. 13, 2024

Hydrochloric acid (HCl) is abundantly generated as the byproduct in chemical industry. The recycling of chloride from HCl related to intensive energy input and resource consumption. European Commission Joint Research Centre stated that production utilization chlorine are indicative development level To utilize a green way, an unprecedented, straightforward, simple electrosynthesis method has been employed produce chlorinated aromatics. control experiments indicated reaction underwent free radical pathway mass transfer was crucial for reaction. Further, microchannel flow electroreactor further used scale up overcome hydrophobic obstacle graphite electrode surface, hydrophilic modification with nitric used. After modification, content O element increased 1.1 2.3%, C–O–C unit 10.9 16.2%, O–C═O 27.1 28.2%. Thus, desired product afforded satisfactory yields under modified electrode.

Язык: Английский

Процитировано

3