Dual Nickel/Photoredox‐Catalyzed Synthesis of N‐formyl N,N’‐Diaryl Ethylenediamines via Multiple C−N/C−C Coupling of Nitroarenes with Trimethylamine DOI
Tongtong Zheng, Zhe Chuan Feng, Jun‐An Ma

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(14), P. 2377 - 2384

Published: June 21, 2023

Abstract N , ’‐Diaryl ethylenediamines are common feedstocks in organic synthesis and important structural motifs medicinal chemistry. Whereas the C−N formation reactions based on anilines aryl halides most direct methods to access ’‐diaryl ethylenediamines, photocatalytic synthetic version remains undeveloped. Herein we describe dual nickel/photoredox‐catalyzed amination reaction using nitroarenes trimethylamine as substrates. This cascade transformation hinges multiple C−C coupling events nitrogen radical α‐aminomethyl derived from nitroarene trimethylamine, respectively. A variety of ‐formyl can be obtained under protocol. Subsequent hydrolysis offers for further derivatizations.

Language: Английский

Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer DOI Creative Commons
Filip S. Meger, John A. Murphy

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

Citations

29
Photocatalytic Hydrogen Atom Transfer-Induced Arbuzov-Type α-C(sp3)–H Phosphonylation of Aliphatic Amines DOI Open Access
Zhexuan Lei, Weigang Zhang, Jie Wu

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16105 - 16113

Published: Dec. 5, 2023

Despite remarkable progress in photocatalytic hydrogen atom transfer (HAT)-induced C(sp3)–H functionalization, achieving to C(sp3)–P transformation by the HAT process remains highly challenging due P-reagents' compatibility issues. α-Aminophosphonic acids have shown great potential medicinal chemistry, yet their synthesis is hindered limited substrate scopes, poor functional group tolerance, and reliance on prefunctionalized substrates, restricting broad applications. Herein, we report HAT-induced α-C(sp3)–H phosphonylation of aliphatic amines, providing rapid access structurally diverse α-aminophosphonates from abundant amines. Leveraging intramolecular HAT, radical polar crossover, an Arbuzov-type cascade, challenges associated with were overcome. This protocol features base-free, redox-neutral, mild conditions employing amines as limiting reagents, allows for late-stage complex drug molecules possessing amine moieties.

Language: Английский

Citations

28
General and selective metal-free radical α-C–H borylation of aliphatic amines DOI Creative Commons
Sumon Sarkar,

Sidhant Wagulde,

Xiangqing Jia

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(11), P. 3096 - 3108

Published: Aug. 22, 2022

Language: Английский

Citations

37
Bismuth vanadate: A versatile heterogeneous catalyst for photocatalytic functionalization of C(sp2)–H bonds DOI

Fan‐Lin Zeng,

Hu-Lin Zhu,

Ru-Nan Wang

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 46, P. 157 - 166

Published: Feb. 23, 2023

Language: Английский

Citations

21
An organophotocatalytic late-stage N–CH3oxidation of trialkylamines toN-formamides with O2in continuous flow DOI Creative Commons
Mark John P. Mandigma, Jonas Žurauskas, Callum I. MacGregor

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(7), P. 1912 - 1924

Published: Dec. 28, 2021

We report an organophotocatalytic, N-CH

Language: Английский

Citations

37
Synthesis of α-tertiary amines by polysulfide anions photocatalysis via single-electron transfer and hydrogen atom transfer in relays DOI Creative Commons
Haoyu Li, Shunsuke Chiba

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(5), P. 1128 - 1142

Published: April 5, 2022

Language: Английский

Citations

27
Multicomponent Construction of Tertiary Alkylamines by Photoredox/Nickel-Catalyzed Aminoalkylation of Organohalides DOI
Tao Yang,

Wenhui Xiong,

Guangyu Sun

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 29177 - 29188

Published: Oct. 12, 2024

Tertiary alkylamines are privileged structural motifs widely present in natural products, pharmaceutical agents, and bioactive molecules, their efficient synthesis has been a longstanding goal organic chemistry. The functionalization of α-amino radicals derived from abundant precursors represents an emerging approach to accessing alkylamines, but application this strategy obtain tertiary remains challenging. Here, we show that dual photoredox/nickel catalysis enables aminoalkylation organohalides (sp

Language: Английский

Citations

6
Photocatalytic Decarboxylative Alkylation of Cyclic Imine–BF3 Complexes: A Modular Route to Functionalized Azacycles DOI
Kamal Bhatt,

Alafate Adili,

Andrew Tran

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Alkyl radicals generated via an acridine photocatalyzed decarboxylation reaction of feedstock carboxylic acids engage with a range cyclic imine-BF

Language: Английский

Citations

5
α‐Amino Radical Halogen Atom Transfer Agents for Metallaphotoredox‐Catalyzed Cross‐Electrophile Couplings of Distinct Organic Halides DOI
Xianhai Tian, Jaspreet Kaur, Shahboz Yakubov

et al.

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(15)

Published: May 19, 2022

α-Amino radicals from simple tertiary amines were employed as halogen atom transfer (XAT) agents in metallaphotoredox catalysis for cross-electrophile couplings of organic bromides with iodides. This XAT strategy proved to be efficient the generation carbon a range partners (alkyl, aryl, alkenyl, and alkynyl iodides). The reactivities these radical intermediates captured by nickel organobromides including heteroaryl, alkyl bromides, enabling six diverse C-C bond formations. Classic named reactions Negishi, Suzuki, Heck, Sonogashira readily achieved net-reductive fashion under mild conditions. More importantly, cross coupling was viable either bromide or iodide limiting reactant based on availability substrates, which is beneficial late-stage functionalization complex molecules. scalability this method batch flow investigated, further demonstrating its applicability.

Language: Английский

Citations

22
Benzoates as photosensitization catalysts and auxiliaries in efficient, practical, light-powered direct C(sp3)–H fluorinations DOI Creative Commons
Shahboz Yakubov, Willibald J. Stockerl, Xianhai Tian

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(47), P. 14041 - 14051

Published: Jan. 1, 2022

Of the methods for direct fluorination of unactivated C(sp3)-H bonds, photosensitization SelectFluor is a promising approach. Although many substrates can be activated with photosensitizing catalysts, issues remain that hamper complex molecules. Alcohol- or amine-containing functional groups are not tolerated, regioselectivity follows factors endogenous to substrate and cannot influenced by catalyst, reactions highly air-sensitive. We report benzoyl serve as efficient photosensitizers which, in combination SelectFluor, enable visible light-powered bonds. Compared previous photosensitizer architectures, benzoyls have versatility function both (i) catalyst simple fluorinations (ii) auxiliaries molecule easily installed removed without compromising yield. Our auxiliary approach substantially decreases reaction's induction period, enables fail under catalytic conditions, (iii) increases kinetic reproducibility, (iv) promotes higher yields, shorter times, on multigram scales, even air. Observations mechanistic studies suggest an intimate 'assembly' prior/after photoexcitation. The allows other EnT photochemistry Examples show how placement proximally directs regioselectivity, where substrate-directed.

Language: Английский

Citations

22