Mechanistic Insights into Enantioselective C(sp3)−H Acylation to Construct α‐Amino Ketones via Photoredox and Ni(II) Dual Catalysis: A DFT Study DOI
Ran Liu, Kang Lv, Xiaoguang Bao

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(8)

Published: March 5, 2023

The development of the merger a Ni(II) catalyst with an appropriate photocatalyst under visible-light irradiation provides new strategy for realizing direct functionalization C(sp3 )-H bonds. Mechanistically, whether reduction Ni to form Ni(0) species is necessary in dual catalysis still remains debate. Herein, DFT calculations were carried out gain mechanistic insight into enantioselective acylation α-amino bonds furnish ketones via photoredox and catalysis. A feasible pathway Ni(I)-Ni(III)-Ni(II)-Ni(III)-Ni(I) cycle suggested sequential elementary steps oxidative addition, single electron reduction, radical reductive elimination leading final product, whereas nickel catalytic cycle, Ni(I)-Ni(0)-Ni(II)-Ni(III)-Ni(I), might not be dual-catalyzed origin stereoselectivity this reaction also discussed, which could attributed minimization steric hindrance between alkyl moiety part phenyl group chiral ligand.

Language: Английский

Synergistic Photoenzymatic Anti-Markovnikov Hydroarylation of Olefins via Heteroaryl Radical Intermediates DOI
Prasun Mukherjee,

Zayed Alassad,

Todd K. Hyster

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Heteroaromatic alkylations are indispensable reactions for synthesizing biologically active molecules. The anti-Markovnikov hydroarylation of olefins using heteroaryl halides furnishes the product as a single regioisomer; however, catalytic variants ineffective at controlling stereochemical outcome these reactions. Here, we report synergistic photoenzymatic flavin-dependent "ene"-reductases with ruthenium photoredox catalysts. Enzyme homologues were identified, which provide access to both enantiomers in greater than 80% yield up 99:1 er. This method is effective styrenyl- and unactivated alkenes, highlighting generality this approach. highest yielding system involves carboxylated photocatalyst increased affinity enzyme. work expands types radical intermediates that enzymes can use stereoselective intermolecular coupling

Language: Английский

Citations

0
Decarboxylative cyanation and thiocyanation via catalytic electron donor-acceptor complex with copper catalysis DOI
Hongping Zhao, Xiaoxiang Xi, Tianbao Wu

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(9), P. 3019 - 3028

Published: Aug. 12, 2024

Language: Английский

Citations

3
Advancements in organocatalysis for radical-mediated asymmetric synthesis: A recent perspective DOI
Fuxing Yang, Tao Huang, Yu‐Mei Lin

et al.

Chem Catalysis, Journal Year: 2023, Volume and Issue: 4(4), P. 100812 - 100812

Published: Nov. 20, 2023

Language: Английский

Citations

8
Visible light-induced denitrogenative annulation reaction of 1,2,3-benzotriazin-4(3H)-ones with alkenes and alkynes via electron donor–acceptor (EDA) complex formation: a sustainable approach to isoindolinone and isoquinolinone synthesis DOI
Ramaraju Korivi, Popuri Sureshbabu, Kumar Babu Busi

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(21), P. 6184 - 6193

Published: Jan. 1, 2024

An efficient metal-free approach for the synthesis of isoindolinones and isoquinolinones from 1,2,3-benzotriazin-4(3 H )-ones via electron donor–acceptor (EDA) complex formation under visible light is described.

Language: Английский

Citations

2
Visible-light-driven oxidation of organosilanes by a charge-transfer complex DOI
Yixuan Chen, Juntao He,

Mei‐Chun Wu

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(43), P. 6588 - 6591

Published: Jan. 1, 2023

Direct oxidation of organosilanes is one the most straightforward ways to access silanols. Herein, we describe a novel photo-induced strategy for silanols, promoted by photoactive charge-transfer complex (CTC) between sodium benzenesulfinate and molecular O2. A streamlined sequence transformation silyl ethers was also readily achieved. This developed protocol represents first example CTC-based organosilanes, offering facile approach series silanol ether products.

Language: Английский

Citations

6
Developments in Visible Light Catalyzed Asymmetric Minisci Reactions DOI
Wenya Li, Yu Wang,

Jiangqi Chen

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(7), P. 2110 - 2110

Published: Jan. 1, 2024

Language: Английский

Citations

1
Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Unactivated Alkenes with α-Pyridyl Alkyl Electrophiles DOI

Yiting Hao,

Xinlin Wang, Yumeng Wu

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(23), P. 15633 - 15640

Published: Nov. 20, 2023

Methods for the synthesis of chiral organic compounds bearing pyridyl-substituted stereogenic centers are great interest to agrochemical, pharmaceutical, and synthetic laboratories in their search unique entities. Here, a concise modular method enantioconvergent hydroalkylation widely available alkenes introduce C(sp3) has been established via nickel/Box catalyst with α-pyridyl alkyl bromide. The mild reaction conditions enable remarkably broad substrate scope good functional-group tolerance, leading formation variety enantioenriched alkylated pyridine derivatives yields high enantioselectivities. Further application is demonstrated by an asymmetric Si–H bond insertion, leveraging productive utility this strategy.

Language: Английский

Citations

3
Visible‐Light‐Driven Heterocyclic Fluoroalkylation Via Electron Donor−Acceptor Complexes DOI
Yufei Li, Kaili Xie,

Shimin Yang

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(20)

Published: June 26, 2024

Abstract Heterocyclic fluoroalkylation is initiated through a photochemical reaction involving an electron donor–acceptor complex. The proceeds smoothly without requiring photocatalyst, transition metal catalyst or additional oxidant. Through extensive experiments, we optimised the heterocyclic method and confirmed its versatility effectiveness on various substrates. process synthesises fluoroalkylated quinoxalinones indolones with high efficiency was successfully extended to gram‐scale applications, highlighting practical utility. Detailed mechanistic analyses, supported by density functional theory calculations elucidated role of complexes deciphered distinct radical chain mechanism inherent in halogen‐atom transfer pathway. Given importance fluoroalkyl groups pharmaceuticals, this simple efficient promises substantial applications medicinal chemistry materials science.

Language: Английский

Citations

0
Visible Light-Induced Oxy-perfluoroalkylation of Olefins via Ternary Electron Donor–Acceptor Complexes DOI
Chuanwang Liu,

Yanman Huo,

Jiawei Bu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10805 - 10815

Published: July 15, 2024

Perfluoroalkyl iodides generally formed electron donor-acceptor (EDA) complexes by halogen bonding with a nitrogen atom containing Lewis bases. Since the electronegativity of oxygen is stronger than that atom, resulting Rf-I···O-type EDA complex less inclined to undergo transfer. Here, we reported rare ternary among perfluoroalkyl iodide, and base. Mechanism experiments density functional theory theoretical (DFT) calculations indicated base-promoted proton-coupled transfer (PCET) process was involved in this photochemical reaction. The intracomplex event generated two radical species, TEMPO radical, enabling subsequent oxy-perfluoroalkylation olefins.

Language: Английский

Citations

0
Radical electrophilic aromatic substitution of electron-deficient aryl halides via aerobic ternary electron donor-acceptor photocatalysis DOI Creative Commons

Jiayi Gu,

Yingfen Meng,

Zhuo Cheng

et al.

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(10), P. 102230 - 102230

Published: Oct. 1, 2024

Highlights•Ternary EDA exciplex induced alkyl aryl ether synthesis•Aerobic photocatalytic system•Good functional group compatibility and late-stage functionalization•Scalable synthesis of fine chemicalsSummaryThe direct use molecular oxygen as a clean, abundant, readily available reactant is one the green, sustainable, yet challenging methodologies for C–O bond construction to access diverse oxygenated compounds. Herein, we report ternary electron donor-acceptor complex system that utilizes O2 construct multiple bonds successively in single-step operation, enabling facile assembly ethers. Mechanistic investigation shows halide/2-tert-butyl-1,1,3,3-tetramethylguanidine/tetrahydrofuran generated situ plays an essential role, affording radical anion species captured by electrophilic form Meisenheimer-type intermediate, subsequently participates Williamson etherification process give products with good selectivity compatibility. This protocol not only enables rapid ethers but also allows chemicals, such proparacaine, decylparaben, sildenafil subunits, starting from halogenated compounds.Graphical abstract

Language: Английский

Citations

0