Review
Chemistry, Multidisciplinary
Kelvin Li, Darryl Fong, Eric Meichsner, Alex Adronov
Summary: Efficient reactions driving progress in synthetic chemistry focus on mild conditions, no by-products, and rapid completion. The strain-promoted azide-alkyne cycloaddition has gained popularity in organic synthesis, bioorthogonal chemistry, and polymer chemistry, leading to significant achievements in producing various polymeric constructs for diverse applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Biochemistry & Molecular Biology
Yaqi Zhao, Zhengqi Chai, Qingrui Zeng, Wen-Xiong Zhang
Summary: Nowadays, the click reaction of azides with alkynes has rapidly evolved as an efficient method for synthesizing 1,2,3-triazoles, an important class of N-containing heterocycles. While the 1,4-selective click reaction is well-established, the corresponding 1,5-selective reaction remains less explored, lacking a systematic review. This timely review summarizes the discovery and development of 1,5-selective click reactions of azides with alkynes for synthesizing 1,5-substituted 1,2,3-triazoles, including three types of reactions based on critical reactive intermediates and related mechanistic studies.
Article
Chemistry, Multidisciplinary
Menghan Cui, Changhui Su, Rong Wang, Qing Yang, Chunxiang Kuang
Summary: This novel and green route involves the direct synthesis of vinyl triazole derivatives with alkynes and triazoles promoted by an inorganic base under transition metal-free conditions, showing great catalytic activity for the anti-Markovnikov stereoselective hydroamination of alkynes. Good yields with excellent functional group tolerance are successfully achieved for a range of substrates, making it an advanced concept for the synthesis of alkenyl triazole with a versatile and cost-efficient approach.
Article
Chemistry, Organic
Jose Laxio Arenas, Pascal Retailleau, Jean-Michel Gillet, Nour-Eddine Ghermani, Sandrine Ongeri, Benoit Crousse
Summary: The 5-fluoro triazole amino acid scaffold prepared by halogen exchange was successfully incorporated into peptides. The X-ray diffraction results revealed an important localization of the 5-fluoro triazole motif on one side of the negative potential surface, with the fluorine atom showing a cylindrical shape in its electron density deformation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Cong Guan, Jiabin Yin, Jian Ji, Jinhua Liu, Xiang Wu, Tong Zhu, Shunying Liu
Summary: A regioselective electrochemical C-H amination method using easily accessible ethers has been developed to synthesize N (2)-substituted 1,2,3-triazole. Multiple substituents, including heterocycles, were well-tolerated, and 24 examples were obtained in moderate to good yields. Control experiments and DFT calculations revealed that the electrochemical synthesis occurs through a N-tosyl 1,2,3-triazole radical cation process, promoted by single-electron transfer from the lone pair electrons of the aromatic N-heterocycle, and the desulfonation is responsible for the high N (2)-regioselectivity.
Article
Chemistry, Organic
Juliana R. Alexander, Paul Kevorkian, Joseph J. Topczewski
Summary: The Banert cascade reaction of propargylic azides can be promoted by simple silver salts, leading to the formation of various indoles and electron-rich heterocycles. The correlationship between the Mayr nucleophilicity parameter (N) and the reaction efficiency enables the formation of C-sp(3)-C-sp(2) and C-sp(3)-C-sp(3) bonds under otherwise identical conditions from structurally dissimilar nucleophiles.
Article
Chemistry, Organic
Andrey Bubyrev, Ksenia Malkova, Grigory Kantin, Dmitry Dar'in, Mikhail Krasavin
Summary: A three-component synthesis of 1,5-disubstituted 1,2,3-triazoles can be achieved from alpha-acetyl-alpha-diazomethane sulfonamides, primary aliphatic amines, and aromatic aldehydes. The synthesis can proceed in two alternative variants based on the substitutions in the diazo reagent. Depending on the variant, the intermediates are either isolated and subjected to aromatization, or both transformations take place in a single step at room temperature.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bidyutjyoti Dutta, Anirban Garg, Parmita Phukan, Akshay Kulshrestha, Arvind Kumar, Diganta Sarma
Summary: The green protocol utilizing the bifunctional ionic liquid as a catalyst, combined with microwave irradiation for rapid synthesis of 5-amino-1,2,3-triazoles, is a novel approach. The experimental results confirm the low environmental impact and greener attributes of this method.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Linwei Zeng, Jiaming Li, Sunliang Cui
Summary: In this study, we report a rhodium-catalyzed enantioselective click cycloaddition of azides and alkynes, which allows for the rapid and modular synthesis of atropisomeric triazoles with excellent yields and enantioselectivities. The process is mild, efficient, scalable, and has a broad substrate scope.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Yawen You, Qingqing Deng, Yibo Wang, Yanjuan Sang, Guangming Li, Fang Pu, Jinsong Ren, Xiaogang Qu
Summary: This study reports on a DNA-based biocompatible, highly efficient, and precisely targeted copper nanocatalyst, which exhibits excellent catalytic activity and achieves efficient prodrug activation and antitumor effects in cancer cells.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Miguel Villarreal-Parra, Gabriel E. Di Gresia, Guillermo R. Labadie, Margarita M. Vallejos
Summary: The mechanisms of the asigmatropic and prototropic reactions in the Banert cascade were investigated using density functional theory, quantum theory of atoms in molecules, and natural bond orbital approaches. The calculated energy barriers were consistent with experimental data. The distribution of electron density on transition structures reflected the behavior of reactants in the Banert cascade. The conjugative effects and charge accumulation at the C(3) atom of propargylic azides were found to be related to the activation energies of sigmatropic and prototropic reactions, respectively. These results allow for the prediction of reaction course by evaluating reactants.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Abdul Wahab, Ziwei Gao, Jing Gou, Binxun Yu
Summary: Triazole phosphonates are important structural motifs in chemical biology and have gained increasing interest in recent years. A novel method to synthesize triazolyl phosphonates starting from furfuryl phosphonate alcohols and organo-azides using an intermolecular copper-catalyzed cascade reaction was developed. A three-component reaction strategy was realized for rapid access to triazole phosphonates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian Ji, Cong Guan, Qinghua Wei, Xuwen Chen, Yun Zhao, Shunying Liu
Summary: This study developed a highly regioselective synthesis of N-2-substituted 1,2,3-triazoles using N-sulfonyl-1,2,3-triazoles and alkyl bromides/alkyl iodides at room temperature. The mechanistic pathway proposed explains the high N-2 regioselectivity, and the protocol showed good to excellent product yields (72-90%).
Article
Chemistry, Organic
Pengfei Sun, Weiguo Wang, Jilong Lai, Huang Yan, Chen-Ho Tung, Zhenghu Xu
Summary: We developed a new multicomponent copper(i)-catalyzed reaction for the synthesis of multi-substituted triazole sulfides from elemental sulfur. The generation of an active electrophilic sulfuration reagent from elemental sulfur is the key feature of this method. By intercepting the click intermediate with a sulfur electrophile formed in situ, we achieved the modular synthesis of 5-thio and 5-selenotriazoles, including various medium-sized cycles and macrocycles, with absolute regioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Xue Li, Haohua Chen, Qingqing Xuan, Shaoyu Mai, Yu Lan, Qiuling Song
Summary: Inspired by the body circulation of Omeprazole, a novel carbenetriggered cascades for synthesizing 2-aminobenzofuran derivatives from N-sulfonyl-1,2,3-triazoles or benzothioazole-bearing thiocarbamates was disclosed, representing an unprecedented imine derivative migration process. Additionally, desulfurizing reagent-free Barton-Kellogg-type reactions starting from N-sulfonyl-1,2,3-triazoles were achieved for the first time, with elemental sulfur confirmed as a byproduct. Experimental data and DFT calculations further explained the unique reactivity observed in these reactions.
