Iron-Mediated Segment Coupling of Alkenols with Acceptors via C–C Radical Translocation and Remote Oxidative 1,5/6-Hydrogen Atom Transfer DOI
Santosh J. Gharpure, Rupali S. Chavan, Dipak J. Fartade

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 9920 - 9925

Published: Nov. 8, 2024

Iron-mediated segment coupling followed by oxidative 1,5/6-hydrogen atom transfer (HAT) for synthesis of ε-oxo alkene derivatives is developed. This transformation involved translocation the radical from H-to-C-to-C-to-C oxidation under MHAT conditions providing rapid access to 1,6/1,7-keto functionalized esters/ketone/sulfones/phosphonates/arenes. The different outcomes with acceptors could be explained bond dissociation energies (BDEs), and mechanistic insights were gained through control experiments, including deuterium labeling studies.

Language: Английский

Fluorine‐Effect‐Enabled Photocatalytic 4‐Exo‐Trig Cyclization Cascade to Access Fluoroalkylated Cyclobutanes DOI
Yulu Zhou, Zhenhua Wu, Jinming Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 13, 2024

Abstract Cyclobutanes are popular structural units in bioactive compounds and versatile intermediates synthetic chemistry, but their synthesis is challenging owing to high ring strain. In this study, a novel method for highly regio‐ diastereoselective of fluoroalkylcyclobutanes bearing vicinal quaternary tertiary stereocenters realized by photocatalytic 4‐exo‐trig cyclization cascade thioalkynes or trifluoromethylalkenes. Density functional theory calculations reveal that unique fluorine effect, arising from hyperconjugative π→σ* C‐F interactions, accounts the regio‐reversed radical addition at sterically hindered alkene carbon, which facilitates an unprecedented closure. This chemistry enables direct controllable construction medicinally valuable quaternary‐carbon‐containing cyclobutanes readily available raw materials, nicely complementing existing methods.

Language: Английский

Citations

5
Controllable Synthesis of Cyclopenta[b]indolines via Photocatalytic Fluoroalkylative Radical Cyclization Cascade of Ynamides DOI
Ji Li, Yulu Zhou,

Jinmin Luo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4643 - 4647

Published: May 29, 2024

A de novo method for direct construction of cyclopenta[b]indolines via a photocatalytic fluoroalkylative radical cyclization cascade ynamides has been established, which proceeds sequence addition, 1,5-HAT, 5-endo-trig cyclization, intramolecular arylation, and oxidative deprotonation. This protocol allows the controllable assembly tricyclic architecture with three contiguous stereocenters, showcasing its high efficiency, compatibility, regio- diastereoselectivity accessing pharmacologically significant fluoroalkylated cyclopenta[b]indolines. It represents one very few examples tetrafunctionalization alkynes.

Language: Английский

Citations

5
Recent Advances in Visible Light Induced Radical 1,2-Functionalization of Alkynes DOI

Kangkui Li,

Xianyang Long,

Yue Huang

et al.

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(6), P. 658 - 658

Published: Jan. 1, 2024

Language: Английский

Citations

4
Photoredox-Mediated Radical Addition/Cyclization To Construct Benzannulated 6,5-Spiroketal Glycosides DOI
Chen Li, Shouyun Yu

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

We herein present a green and mild photoredox strategy for constructing framework of benzannulated 6,5-spiroketal glycosides. This method employs various O-arylacetylene glycosides aryl ketone acids as the starting materials, facilitating rapid straightforward synthesis with up to 92% yields under catalytic conditions. efficient approach has potential significantly enhance molecular library carbohydrate-based pharmaceuticals.

Language: Английский

Citations

0
Mechanisms of C(sp3)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation DOI
Bin Chen,

Tiantian Feng,

Da‐Gang Zhou

et al.

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The mechanisms for the C(sp3)-H activation and addition reactions between acetonitrile (or acetone) alkynes have been investigated with M06-2X-D3/ma-def2-TZVP method basis set. SMD (solvation model based on solute electron density) was applied to simulate solvent effect. In first second reactions, 2-phenylbut-3-yn-2-ol reacted acetone, respectively. First, activations of acetone could be achieved by PhCOO• t-BuO• radicals. Then, converted into final products P1 P2. Gibbs free energy surfaces these two suggest that blue lines would favorable paths lower barriers, terminal C atom C≡C bond is best reactive site. Moreover, analysis IRI (Interaction Region Indicator) reveals Z- E-configuration transformations. While in third fourth methyl(2-(phenylethynyl)phenyl)sulfane has interactions via some paths, profiles show C10 atom, rather than C11 priority, are favorable. Furthermore, action mode Na2HPO4 reduce barrier benefit reaction. vdW (van der Waals) play an important role choice fifth sixth) reaction, it happened 1-(2-(methylthio)phenyl)-3-phenylprop-2-yn-1-one acetontrile yield product P5 P6). computational results uncovered line path, site depends interactions, which origin selectivity. addition, investigation byproducts carried out, can explain reason only main produced. Both those agree experimental results. localized orbital locator (LOL) isosurfaces, Laplacian order (LBO), density critical point (ρBCP), spin isosurface graphs, graphs used analyze structure reveal reaction substances.

Language: Английский

Citations

0
Dual anion and cation catalysis enabled by an ion-pairing photocatalyst DOI

Xi-Xian Chen,

Xiang Chen,

Feng Lan

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A dual catalysis involving both anionic and cationic species of an ion-pairing photocatalyst is achieved. By adopting this mode action, photocatalytic hydrogen transfer cross-coupling reactions can be enabled using a single photocatalyst.

Language: Английский

Citations

0
Photocatalytic [3+2] Cycloaddition of Alkyl/aryl Iodides and Internal Alkynes by Merging Halogen and Hydrogen Atom Transfer DOI Creative Commons
Zhenyu Gu,

Rong Jia,

Tianqing Zeng

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(19), P. 2329 - 2334

Published: May 22, 2024

Comprehensive Summary A visible light photocatalytic [3+2] cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein. By merging halogen atom transfer (XAT) and hydrogen (HAT), alkyl/aryl serve a formal diradical precursor add across C‐C triple bonds to deliver number functionalized cyclopentanes in moderate high yields exceptional regio‐ diastereoselectivity. reductive radical‐polar crossover mechanism, involving cascade XAT, radical addition, 1,5‐HAT, polar effect‐promoted 5‐endo annulation, single electron (SET) reduction, protonation, may account for this unprecedented dehalogenative cycloaddition. This work not only expands repertoire traditional RATC methodology, but also provides robust platform expedient assembly cyclopentanes, valuable structural motif realms medicinal chemistry material sciences.

Language: Английский

Citations

2
Photoredox-Catalyzed Synthesis of 3,3-Difluoro-γ-lactams via 1,5-Hydrogen Atom Transfer-Involved Alkyne Difunctionalization and C–N Cleavage DOI
Lin Tang,

Fengjuan Jia,

Ge Lv

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 9903 - 9908

Published: Nov. 8, 2024

This manuscript describes the application of a 1,5-hydrogen atom transfer strategy in photoredox-catalyzed hydrodifluoroalkylation alkynes. The approach utilizes sequential cascade process difluoroalkylation, transfer, C(sp

Language: Английский

Citations

2
One‐Pot Reactions of Ynones with Isothiocyanates for Accessing 2‐Aminothiophenone and Indole‐Fused/Indole‐Substituted Thiophenone Derivatives DOI

Zefeng Jin,

LI Cui-ying,

Guodong Shen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(24), P. 5151 - 5159

Published: Aug. 29, 2024

Abstract A copper or silver‐catalyzed cascade addition/5‐ exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis a variety ( Z )‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives diverse substitutions in single vessel. The method is featured pot‐economy as well regio‐ and ‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, relevant indole‐fused indole‐substituted thiophenone were also assembled one pot by merging other bond formation methods. Based on experiments related reports, pathway triggered addition ynone‐derived radical towards C( sp )‐atom was proposed to elucidate probable process transformation.

Language: Английский

Citations

0
Manganese‐ Mediated Cascade Radical Oxidative Cyclization/1,6‐Conjugate Addition of Unsaturated Oximes with p‐Quinone methides: Facile Access to β,β‐Diarylmethine Isoxazolines DOI Open Access

Vijay Vara,

Kishor R. Thete,

Ganesh S. Ghotekar

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 9, 2024

A simple and efficient strategy for the synthesis of structurally diverse β,β-diarylmethine substituted isoxazoline derivatives have been developed. This approach employs a manganese-promoted oxidative cyclization coupled with 1,6-conjugate addition unsaturated oximes to p-quinone methides. The key features this study include formation C-O C-C bonds through intramolecular intermolecular interactions, facilitated by in situ generated iminoxyl radicals. isoxazolines, bearing wide range functional groups, were isolated high yields.

Language: Английский

Citations

0