Photoredox‐Enabled Manganese‐Catalyzed [2+2+2] Cycloaddition of Alkynes DOI
Yi Zhou, Yongqin He, Xiaoyu Wang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1545 - 1550

Published: Feb. 8, 2024

Abstract Manganese (Mn) is the third most abundant transition metal on Earth and known for its exceptional biocompatibility. The development of novel catalytic mode Mn great significance to advancing organic synthesis. In this study, first manganese (Mn)‐catalyzed [2+2+2] cycloaddition alkynes achieved with aid visible‐light photoredox catalysis. Photoredox catalysis proposed promote transformation by in situ reduction high‐valent Mn(II) complex Mn(0) species, thereby initiating reaction. Additionally, a photooxidation‐induced reductive ellimination step also suggested. This system further distinguished notable tolerance towards both terminal internal as counterparts diynes.

Language: Английский

Photocatalytic hydrofluoroalkylation of alkenes with carboxylic acids DOI

Kang‐Jie Bian,

Yen‐Chu Lu, David Nemoto

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(12), P. 1683 - 1692

Published: Nov. 13, 2023

Language: Английский

Citations

77

Photoinduced Hydrodifluoromethylation and Hydromethylation of Alkenes Enabled by Ligand-to-Iron Charge Transfer Mediated Decarboxylation DOI

Xu-Kuan Qi,

Li-Juan Yao,

Mengjie Zheng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1300 - 1310

Published: Jan. 11, 2024

Directly utilizing abundant and inexpensive sources of aliphatic carboxylic acids is highly attractive for the synthesis CF2H- CH3-containing compounds. Herein, we report a versatile photoinduced iron-catalyzed platform hydrodifluoromethylation hydromethylation alkenes without need additional stoichiometric oxidants. These two transformations are accomplished by visible-light-induced ligand-to-iron charge transfer open-shell activation system using industrial chemical difluoroacetic acetic as precursors postulated to operate via difluoromethyl methyl radical-mediated decarboxylation mechanism. Experimental results show that strategy also applicable difunctionalization unactivated alkenes. Meanwhile, this provides viable route pharmaceutically active molecules containing deuterated units. The protocol exhibits several features, including mild reaction conditions, divergent radical precursors, operational simplicity scalability, good chemo- regioselectivity, scalability supported continuous flow technology, ability provide high-value building blocks applications in one step.

Language: Английский

Citations

39

Continuous Flow Decarboxylative Monofluoroalkylation Enabled by Photoredox Catalysis DOI Creative Commons

F Pasca,

Yuri Gelato,

Michael Andresini

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 684 - 692

Published: Feb. 2, 2025

Herein, we report a scalable and mild strategy for the monofluoroalkylation of wide array Giese acceptors via visible-light-mediated photoredox catalysis in continuous flow. The use flow technology significantly enhances productivity scalability, whereas mildness conditions functional group tolerance are ensured by leveraging 4CzIPN, transition-metal-free organic photocatalyst. Structurally diverse secondary tertiary monofluoroalkyl radicals can thus be accessed from readily available α-monofluorocarboxylic acids. Given reaction conditions, this protocol is also amenable to late-stage functionalization biologically relevant molecules such as menthol, amantadine, bepotastine, estrone derivatives, rendering it suitable application drug discovery programs, which introduction fluorinated fragments highly sought after. This method was extended enable reductive multicomponent radical-polar crossover transformation rapidly increase complexity assembled architectures single synthetic operation.

Language: Английский

Citations

4

Iron-mediated ligand-to-metal charge transfer enables 1,2-diazidation of alkenes DOI Creative Commons
Muliang Zhang, Jinghui Zhang, Qingyao Li

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 23, 2022

Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well privileged molecular catalysts, an efficient practical strategy that avoids use stoichiometric strong oxidants is highly desirable. We herein report application ligand-to-metal charge transfer (LMCT) excitation to 1,2-diazidation reactions from alkenes TMSN

Language: Английский

Citations

42

Photoinduced activation of alkyl chlorides DOI
Cheng‐Long Ji,

Xinyi Zhai,

Qing-Yun Fang

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(17), P. 6120 - 6138

Published: Jan. 1, 2023

In recent years, the activation of unactivated alkyl chlorides through light-induced processes has emerged as a promising field in radical chemistry, and led to new transformations organic synthesis. Direct utilization C(sp3)-hybridized electrophiles enables facile construction carbon-carbon carbon-heteroatom bonds. Furthermore, studies medicinal chemistry indicate that their presence is associated with high levels success clinical trials. This review summarizes advances photoinduced discusses mechanistic aspects underlying these reactions. We anticipate this will serve valuable resource for researchers chemical bond functionalization, inspire considerable developments drug synthesis, materials science other related disciplines.

Language: Английский

Citations

37

Regiodivergent electroreductive defluorinative carboxylation ofgem-difluorocyclopropanes DOI
Bin Zhao,

Zichen Pan,

Jiayu Pan

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(8), P. 3095 - 3102

Published: Jan. 1, 2023

A regiodivergent electrochemical defluorocarboxylation of gem -difluorocyclopropanes is realized, providing access to branched and linear carboxylated monofluorinated alkenes.

Language: Английский

Citations

30

Visible light-initiated manganese-catalyzed hydrosulfonylation of alkenes DOI
Chunmin Li,

Xin-Xin Dong,

Zhe Wang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(10), P. 4122 - 4128

Published: Jan. 1, 2023

A visible light-initiated manganese-catalyzed radical hydrosulfonylation of a wide range structurally diverse alkenes using commercially available and relatively cheap sulfonyl chlorides as sources is described.

Language: Английский

Citations

24

Silver-Promoted Three-Component Synthesis of Perfluoroalkenyl Pyrroles through Partial Defluorinative Functionalization of Perfluoroalkyl Halides DOI
Wenjun Ji, Wei Han,

Yuanyuan Ren

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6197 - 6202

Published: July 15, 2024

A silver-promoted three-component heterocyclization of alkynes, perfluoroalkyl halides, and 1,3-dinucleophiles was developed for the efficient synthesis privileged (E)-perfluoroalkenyl pyrroles. The reaction proceeded through a rationally designed sequence radical perfluoroalkylation intramolecular defluorinative [3 + 2]-heterocyclization. utility halide as perfluoroalkenyl reagent, by selective controllable functionalization two inert C(sp3)–F bonds at vicinal carbon centers on chain, provides new mode value-added organofluorides starting from easily available low-cost fluorinated feedstock.

Language: Английский

Citations

11

Modular three-component radical fluoroalkyl-sulfuration of unactivated alkenes DOI

Gao-feng Yang,

Zhi Liu, Kai Liu

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2025, Volume and Issue: 69, P. 249 - 258

Published: Feb. 1, 2025

Language: Английский

Citations

1

Photoinduced Three-Component Carboarylation of Unactivated Alkenes with Protic C(sp3)–H Feedstocks DOI
Yang Hong,

Meng-Yuan Dong,

Dong‐Sheng Li

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(41), P. 7677 - 7684

Published: Oct. 10, 2022

A general and mild strategy involving three-component carboarylation of unactivated alkenes with protic C(sp3)–H feedstocks via photoredox catalysis was reported. This catalytic system is compatible a broad range alkenes, cyano-substituted arenes, diverse feedstocks. The synthetic value this protocol demonstrated by the late-stage functionalization complex molecules synthesis antiallergies including pheniramine, chlorpheniramine, brompheniramine.

Language: Английский

Citations

36