Article
Chemistry, Organic
Pooja Y. Vemuri, Frederic W. Patureau
Summary: In this study, an unprecedented, simple and hetero-selective cross-dehydrogenative N-N coupling of amides and benzotriazoles using a hypervalent iodine species as the terminal oxidant was reported. The scope and mechanistic investigations of this reaction were discussed.
Review
Chemistry, Multidisciplinary
Alexis Tabey, Pooja Y. Vemuri, Frederic W. Patureau
Summary: The high electronegativity of nitrogen presents challenges for N-N bond forming cross-coupling reactions, especially in an intermolecular fashion. Dehydrogenative N-N coupling reactions are advantageous in terms of step and atom economy, but require careful design of an oxidizing system to avoid unwanted side reactions. Despite the importance of N-N bonds in organic chemistry, only a few intermolecular hetero N-N cross-dehydrogenative couplings exist, highlighting the need for further research in this area.
Review
Chemistry, Multidisciplinary
Jianbin Li, Chia-Yu Huang, Chao-Jun Li
Summary: This review summarises recently developed strategies for achieving C-C cross-couplings between an inert aliphatic C-H bond and another C-H bond through different C(sp3)-H functionalisation tactics.
TRENDS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Mo Chen, Austin M. Ventura, Soumik Das, Ammar F. Ibrahim, Paul M. Zimmerman, John Montgomery
Summary: Current methodologies for metal-catalyzed cross-couplings require the installation of reactive functional groups on both reaction partners in advance. In contrast, C-H functionalization approaches show potential in simplifying the substrates required; however, challenges such as low reactivity and similar reactivity of different C-H bonds add complexity. This study describes an oxidative cross dehydrogenative coupling of α-amino C(sp(3))-H bonds and aldehydes to produce ketone derivatives using an unusual reaction medium that simultaneously utilizes di-tert-butyl peroxide as an oxidant and zinc metal as a reductant. The method has a broad substrate scope and offers an attractive approach for accessing α-amino ketones through the formal acylation of C-H bonds adjacent to nitrogen in N-heterocycles. Experimental investigation and computational modeling provide evidence for a mechanistic pathway involving cross-selective nickel-mediated cross-coupling of α-amino radicals and acyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xinyu Chen, Hongqiang Liu, Hui Gao, Pinhua Li, Tao Miao, Hongji Li
Summary: An electrochemical cross-dehydrogenative coupling of indoles with xanthenes has been achieved at room temperature without the need for any catalyst or external oxidant, yielding moderate amounts of indole derivatives. Mechanistic experiments suggest a possible involvement of a radical pathway in this reaction system.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Min Wang, Yicheng Zhang, Xinyu Yang, Peipei Sun
Summary: A direct and convenient strategy for the synthesis of 3-alkylquinoxalin-2(1H)-ones and other alkyl N-heteroarenes has been developed. This strategy involves a photocatalyzed alkylation of quinoxalin-2(1H)-ones and other N-heterocycles using commercially available, low-cost alkanes under ambient conditions, with phenanthrenequinone as the photocatalyst. The transformation offers advantages of an environment-friendly protocol, mild conditions, good functional-group tolerance, and high yields of products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Applied
Ilya N. Egorov, Anindita Mukherjee, Sougata Santra, Dmitry S. Kopchuk, Igor S. Kovalev, Yuanli Liu, Grigory V. Zyryanov, Adinath Majee, Oleg N. Chupakhin, Brindaban C. Ranu
Summary: This review highlights the various applications of cross dehydrogenative coupling reactions under ball milling for the synthesis of useful molecules in a more efficient and convenient manner.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Heng Li, Congcong Qiang, Yujie Liao, Qiao Chu, Ping Liu, Peipei Sun
Summary: In this study, a method for electrochemical cross dehydrogenative coupling (CDC) reaction of heterocycles with ethers mediated by hydrogen atom transfer (HAT) was established. Saturated linear, branched or cyclic ethers were all suitable for this cross-coupling reaction, resulting in the formation of the corresponding products in yields of 70-98%. The advantages of this reaction include transition metal- and chemical oxidant-free conditions, high yields, and broad functional group tolerance, etc.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Shi-Yen Chen, Yan-Hsiang Tseng, Chia-Fang Lu, Chun-Yao Chuang, Yen-Ju Cheng
Summary: A palladium-catalyzed C-2-regioselective direct dehydrogenative alkynylation of unsubstituted selenophene was achieved, followed by C-5-alkynylation of selenophenes substituted with R-1 groups at 2-position. The reaction demonstrated tolerance towards a wide range of functional groups, including electron-withdrawing or electron-donating groups.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xuan Guo, Bing-ru Shao, Wen-feng Jiang, Lei Shi
Summary: A new strategy for cross-dehydrogenative C-C and C-P coupling reaction without the use of a photocatalyst has been developed. This method allows for the synthesis of various 1-substituted tetrahydroisoquinoline derivatives through visible-light direct excitation of substrates. The broad substrate scope demonstrates good synthetic versatility and practicality.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hong Zhang, Zenghui Ye, Na Chen, Zhenkun Chen, Fengzhi Zhang
Summary: An electrochemical method using easily available hydrazones has been developed for the synthesis of 1H-indazoles. This metal- and oxidant-free protocol is compatible with various functional groups and can be carried out on a gram-scale under neutral and mild conditions. The method has been successfully applied to the efficient synthesis of anti-tumor compounds. Mechanism studies suggest the involvement of a radical pathway, with an important role played by HFIP.
Review
Chemistry, Organic
C. M. A. Afsina, Thaipparambil Aneeja, Mohan Neetha, Gopinathan Anilkumar
Summary: Copper-catalyzed organic reactions have attracted widespread attention due to the abundance and affordability of copper, as well as its low toxicity, eco-friendliness, sustainable nature, and versatility as a catalyst. These reactions are primarily used for the synthesis of biologically important nitrogen heterocycles, amines, amides, imines, and alkynes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Wei Wei, Xiaodan Zhao
Summary: The carbon-carbon bond-forming cross-dehydrogenative coupling reaction using organoselenium catalysis involving a high-valent para-methoxyphenyl selenium species has been developed. This method enables the synthesis of alpha,alpha-disubstituted alpha-amino acid derivatives with excellent regioselectivities through vinyl or allylic C-H functionalization. The generality of this method has been demonstrated by the cross-coupling of an alkene with an oxindole and the direct functionalization of electron-rich arenes with azlactones.
Article
Chemistry, Applied
Vikas Dixit, Nidhi Jain
Summary: In this study, a photo-activation method of quinoxalin-2(1H)-ones in visible light without photocatalyst and transition metal catalyst was demonstrated. The photo-activated quinoxalin-2(1H)-one species transfers its energy to oxygen, which promotes C-N cross dehydrogenative coupling with nucleophilic partners. Preliminary studies also showed that the quinoxalin-2(1H)-one-carbazole adducts exhibit fluorescent properties.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Hong-Yu Zhang, Jianjun Chen, Cong-Cong Lu, Ya-Ping Han, Yuecheng Zhang, Jiquan Zhao
Summary: This study describes a cross-dehydrogenative-coupling reaction using visible light and air at room temperature to synthesize aminomethyl-substituted N-heterocycles, providing an efficient, environmentally friendly, and convenient method.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
