Visible-Light-Promoted Fe(III)-Catalyzed N–H Alkylation of Amides and N-Heterocycles DOI
Hangcheng Ni, Chaoming Li,

Xingzi Shi

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 9797 - 9805

Published: July 20, 2022

The combination of the radical chemistry ligand-to-metal charge transfer with metal catalysis by a single iron salt helps to realize visible-light-promoted N-H alkylation amides and N-heterocycles. A wide variety nitrogen-containing heterocycles were tolerated in our protocol give N-alkylated products. applicability this was further demonstrated late-stage N-H-containing pharmaceuticals. Moreover, N-H-alkylated α-amino tetrahydrofurans could be transformed into versatile ring-opened amino alcohols under reducing conditions. mechanistic study revealed that hydrogen atom tert-butoxyl chlorine responsible for activation C(sp3)-H precursors.

Language: Английский

Ligand‐to‐Metal Charge Transfer (LMCT) Photochemistry at 3d‐Metal Complexes: An Emerging Tool for Sustainable Organic Synthesis DOI Creative Commons
Fabio Juliá

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(19)

Published: Aug. 11, 2022

Abstract Despite the rich photochemistry of 3d‐metal complexes, utilization excited‐state reactivity these compounds in organic synthesis has been historically overlooked. The advent photoredox catalysis changed perception synthetic chemists towards photochemistry, and nowadays potential photoinduced, outer‐sphere single‐electron transfer events is widely recognized. More recently, an emerging new mode photoactivation taken spotlight, based on inner‐sphere triggered by population ligand‐to‐metal charge‐transfer (LMCT) excited states. Contrarily to photoredox, LMCT‐activation does not rely matching redox potentials, offers unique profiles particularly well suited Earth‐abundant metal complexes. Those appealing features are propelling development methods using this blueprint generate highly reactive open‐shell species under mild conditions. aim contribution provide a didactical tool for comprehension concept facilitate methodologies achieve sustainable chemical transformations.

Language: Английский

Citations

225
Iron-Catalyzed C(Sp3)–H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer DOI
Jia‐Lin Tu,

Ao-Men Hu,

Lin Guo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7600 - 7611

Published: March 23, 2023

Catalytic C(sp3)-H functionalization has provided enormous opportunities to construct organic molecules, facilitating the derivatization of complex pharmaceutical compounds. Within this framework, direct hydrogen atom transfer (HAT) photocatalysis becomes an appealing approach goal. However, viable substrates utilized in these protocols are limited, and site selectivity shows preference activated thermodynamically favored bonds. Herein, we describe development undirected iron-catalyzed borylation, thiolation, sulfinylation reactions enabled by photoinduced ligand-to-metal charge (LMCT) process. These exhibit remarkably broad substrate scope (>150 examples total), most importantly, all three show unconventional regioselectivity, with occurrence preferentially at distal methyl position. The procedures operationally simple readily scalable provide access high-value products from hydrocarbons one step. Mechanistic studies control experiments indicate that afforded is not only relevant HAT species but also largely affected use boron- sulfone-based radical acceptors.

Language: Английский

Citations

116
A practical FeCl3/HCl photocatalyst for versatile aliphatic C–H functionalization DOI Creative Commons

Zhen-Yao Dai,

Shuo‐Qing Zhang, Xin Hong

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(5), P. 1211 - 1222

Published: April 20, 2022

Language: Английский

Citations

86
Synthetic Applications of Photocatalyzed Halogen‐Radical Mediated Hydrogen Atom Transfer for C−H Bond Functionalization DOI Creative Commons
Stefano Bonciolini, Timothy Noël, Luca Capaldo

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(34)

Published: May 13, 2022

Abstract The opportunity to activate C(sp 3 )−H bonds via homolytic cleavage by means of halogen radicals has long been disregarded in synthetic endeavors due the unpredictable selectivity. Nowadays, photocatalysis established itself as a method choice for generation such reactive intermediates under mild conditions. This Minireview collects recent examples showcasing how photocatalytic manifolds have used tame aggressive Hydrogen Atom Transfer (HAT) purposes. In last section this work, we address site‐selectivity issues posed methodology and show it can be guided through judicious reaction

Language: Английский

Citations

71
Resurgence and advancement of photochemical hydrogen atom transfer processes in selective alkane functionalizations DOI Creative Commons
Liang Chang, Shun Wang, Qing An

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(25), P. 6841 - 6859

Published: Jan. 1, 2023

The selective functionalization of alkanes has long been recognized as a prominent challenge and an arduous task in organic synthesis. Hydrogen atom transfer (HAT) processes enable the direct generation reactive alkyl radicals from feedstock have successfully employed industrial applications such methane chlorination process,

Language: Английский

Citations

67
Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer DOI
Xiaoya Yuan, Congcong Wang, Bing Yu

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(9), P. 109517 - 109517

Published: Jan. 21, 2024

Language: Английский

Citations

33
Anti-Markovnikov hydro- and deuterochlorination of unsaturated hydrocarbons using iron photocatalysis DOI

Kang‐Jie Bian,

David Nemoto, Ying Chen

et al.

Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

Citations

2
Stop-Flow Microtubing Reactor-Assisted Visible Light-Induced Hydrogen-Evolution Cross Coupling of Heteroarenes with C(sp3)–H Bonds DOI
Dong‐Sheng Li, Tao Liu, Yang Hong

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(8), P. 4473 - 4480

Published: March 31, 2022

The synthesis of valuable alkyl-substituted heteroarenes from abundant and inexpensive feedstocks under mild conditions is attractive highly desirable in pharmaceutical natural product synthesis. Minisci-type cross dehydrogenative coupling between C(sp3)–H bonds offers direct access to these important scaffolds a step-economic manner. Herein, assisted by stop-flow microtubing reactors, an operationally simple protocol for the visible light-induced hydrogen-evolution with unactivated was developed metal- external oxidant-free A wide range alkylated generated common feedstock chemicals, including ethane. Mechanistic studies indicated that photoredox-induced hydrogen atom transfer processes followed rearomatization delivered desired products. merits this strategy were further demonstrated late-stage functionalization various complex bioactive molecules.

Language: Английский

Citations

41
Copper-Mediated Dehydrogenative C(sp3)–H Borylation of Alkanes DOI Creative Commons
Ruocheng Sang, Wangyujing Han, Hanwen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15207 - 15217

Published: July 6, 2023

Borylations of inert carbon-hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated involving hydrogen atom transfer pathways have emerged as attractive alternatives because they provide complimentary regioselectivities and proceed metal-free However, net oxidative processes require stoichiometric oxidants therefore cannot compete the high economy their precious-metal-catalyzed counterparts. Herein, we report that CuCl2 catalyzes radical-mediated, C(sp3)-H alkanes bis(catecholato)diboron This is a result an unexpected dual role copper catalyst, promotes oxidation reagent to generate electrophilic bis-boryloxide acts effective borylating agent in subsequent redox-neutral photocatalytic C-H borylations.

Language: Английский

Citations

38
Visible-Light-Mediated Deacylated Alkynylation of Unstrained Ketone DOI
Hao Wu, Shuguang Chen, Dengmengfei Xiao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(7), P. 1166 - 1171

Published: Feb. 14, 2023

Deconstructive alkynylation of an unstrained ketone catalyzed by organic photocatalyst under blue light irradiation is reported for the first time. A broad substrate scope with up to 63 examples, excellent functional group tolerance, and gram scale reaction demonstrated practicality this novel method. The dihydroquinazolinone derivative trifluoroacetophenone had been proved have potential as a trifluoromethylation reagent after working well various alkynyl bromides.

Language: Английский

Citations

29