Review
Multidisciplinary Sciences
Uttam Dutta, Sudip Maiti, Trisha Bhattacharya, Debabrata Maiti
Summary: This review summarizes recent elegant discoveries in controlling distal C-H activation through directing group assistance, transient mediators or traceless directors, noncovalent interactions, and catalyst and/or ligand selection.
Article
Chemistry, Inorganic & Nuclear
Gayathri B. Gange, Amanda L. Humphries, Mark D. Smith, Dmitry V. Peryshkov
Summary: In this study, we report the reactivity of carboranyl diphosphine with terminal alkynes, resulting in the formation of boron-containing phosphacycles. The reaction combines the activation of electron-deficient alkynes by phosphine groups and the redox behavior of carborane clusters, leading to the formation of a fused product of alkenylphosphonium cycle and reduced carborane cluster.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jiaming Cheng, Jie Sheng, Xu Cheng
Summary: In this study, an electrochemical deuteration method using deuterium water in DMF was used to convert aromatic trifluoromethyl to methyl-d(3) groups. The addition of a basic additive was crucial for achieving highly selective reaction, resulting in yields up to 94%, D ratio up to 97%, and CD3 incorporation up to 90%.
Article
Chemistry, Applied
Sofia Strekalova, Alexander Kononov, Vladimir Morozov, Olga Babaeva, Elena Gavrilova, Yulia Budnikova
Summary: This study describes the electrochemical amidation of C(sp2)-H and C(sp3)-H bonds of a wide range of arenes using nitriles as amide sources, achieved under mild conditions without the need for metal catalysts or external oxidizing agents. The method offers moderate to high yields, can be applied to arenes with diverse functional groups, and is suitable for gram scale synthesis. The key role of the hydroxyl radical as an inductor generated during the oxidation of water has been established through EPR experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Jiafeng He, Xun-Shen Liu, Mingjia Li, Shaoting Peng, Zhi-Yao Si, Lu Liu
Summary: A highly stereoselective chalcogenide ylide formation/Smiles rearrangement reaction of diaryl thioether/selenoethers and triazoles catalyzed by Rh(ii) was successfully developed, providing an efficient strategy for constructing trisubstituted acyclic vinyl sulfides/selenides. The key features of this protocol include simple operation, readily available starting materials, atom economy, broad substrate scope, and convenient transformation of products.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Peng Shi, Yongliang Tu, Deshen Kong, Peng Wu, Ding Ma, Carsten Bolm
Summary: FeBr3-catalyzed intramolecular amidations in a ball mill lead to high yields of 3,4-dihydro-2(1H)-quinolinones. The reactions are solvent-free and easy to perform, with no need for additional ligands. Both 4-substituted aryl and beta-substituted dioxazolones provide highly selective products. Mechanistically, the formation of rearranged products is explained by an electrophilic spirocyclization followed by C-C migration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Huili Li, Jianmin Fu, Jundong Fu, Xueji Li, Donglei Wei, Hou Chen, Liangjiu Bai, Lixia Yang, Huawei Yang, Wenxiang Wang
Summary: A visible-light metal-free photocatalytic regioselective and enantioselective alkene halofunctionalization reaction under mild conditions is described. Various terminal and internal alkenes could be transformed to α-halogenated and α,β-dibrominated derivatives with good to excellent yields in as short as 5 min reaction time. Water serves as the green nucleophile and solvent in halohydroxylation and halo oxidation reactions. Different types of products can be obtained by adjusting the reaction conditions. Moreover, sunlight demonstrates the ability to produce similar yields, showcasing a practical example of solar synthesis and offering an opportunity for solar energy utilization.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Li Wang, Qi Zhong, Youliang Zou, Youzhi Yin, Aizhen Wu, Quan Chen, Ke Zhang, Jiachen Jiang, Mengzhen Zhao, Hua Zhang
Summary: Selective carbon-carbon bond activation was achieved through fragmentation borylation mediated by B(OMe)(3)/B(2)pin(2), leading to the formation of two C-B bonds in non-polar unstrained Csp(2)-Csp(3) and Csp(2)-Csp(2) bonds. This new reaction mode is expected to stimulate the development of reactions based on inert C-C bond activation, as suggested by preliminary mechanistic investigations.
Article
Chemistry, Physical
Julianna Mruk, Agata J. Pacula-Miszewska, Leszek Pazderski, Joanna Drogosz-Stachowicz, Anna E. Janecka, Jacek scianowski
Summary: The study presents a solvent-free thermally induced C-N bond formation driven by Au(III) salts, with the reaction products confirmed by various analysis techniques. The derivatives were further tested as catalysts and anticancer agents, showing potential applications in both fields.
Article
Chemistry, Multidisciplinary
Ruben Alvarez-Yebra, Alba Sors-Vendrell, Agusti Lledo
Summary: We introduce a calix[5]arene derived cavitand receptor stabilized in the closed cone conformation through intermolecular hydrogen bonding with methanol. The receptor possesses a highly spherical aromatic surface that can effectively bind C60 and C70 fullerenes, and the binding can be regulated allosterically by methanol addition. A flexible cavitand host based on calix[5]arene for fullerenes is presented, where stabilization through intermolecular hydrogen bonding with methanol leads to a more structured environment and a 10-fold enhancement of the association constant with C60.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Ruben Alvarez-Yebra, Alba Sors-Vendrell, Agusti Lledo
Summary: We present a readily available cavitand receptor based on calix[5]arene, which is stabilized in the closed cone conformer through intermolecular hydrogen bonding with methanol molecules. The receptor has a highly spherical aromatic surface that binds C60 and C70 fullerenes effectively, and the binding event can be regulated by the addition of methanol.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Organic
Qingyao Zhang, Wanqiang Yuan, Yingbo Shi, Fei Pan
Summary: An organophotocatalytic ring opening/remote trifluoromethylselenolation reaction of cycloalkanols is reported. This reaction proceeds via radical ring-opening in a photocatalytic system without metal catalysis under mild conditions, followed by the formation of remote C(sp3)-SeCF3 bond. The reaction shows high yield and compatibility with various aryl cyclic alcohols and different ring systems.
TETRAHEDRON LETTERS
(2022)
Review
Chemistry, Organic
U. S. Kanchana, Elizabeth J. Diana, Thomas V. Mathew
Summary: This review summarizes the latest advancements in nickel-catalyzed C-S bond formation reactions, which have attracted attention due to their wide application and the substitution of toxic metals.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Anirudra Paul, Jae Hyun Kim, Scott D. Daniel, Daniel Seidel
Summary: Despite efforts by practitioners, direct alpha-C-H bond functionalization of unprotected alicyclic amines is rare. A new method utilizing N-lithiated alicyclic amines has been developed, providing a convenient approach to achieve functionalization reactions under mild conditions. This method offers a new pathway for the synthesis of beta-amino ketones with regioselective alpha'-alkylation, and potential for one-pot synthesis of polycyclic dihydroquinolones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Kwan Hong Min, Naeem Iqbal, Eun Jin Cho
Summary: By utilizing a rare bidentate primary aminophosphine ligand, a nickel-catalyzed reductive coupling of alkynes and amides was achieved, leading to the synthesis of highly functionalized indoles containing trifluoromethyl groups, which is of significance in drug research.
Article
Chemistry, Physical
Dong Yeun Jeong, Da Seul Lee, Ha Lim Lee, Sanghee Nah, Jun Yeob Lee, Eun Jin Cho, Youngmin You
Summary: In this research, we investigated the mechanism of radical-ion photoredox catalysis and the generation and annihilation of the key catalytic intermediate in the borylation reaction of aryl halides. Our studies provided convincing evidence that the excited-state radical anion is the active catalyst species. We also found that the catalyst activation is delayed by multiple annihilative processes, with the intrinsic relaxation of the excited-state radical anion being the most destructive.
Article
Chemistry, Organic
Ujjwal Karmakar, Ho Seong Hwang, Yunjeong Lee, Eun Jin Cho
Summary: Visible-light-induced para-selective C-H functionalization of anilines through N-H insertion was achieved using diazomalonates with the assistance of an Ir(III) photocatalyst. The para-selective radical-radical cross coupling occurred through C-centered radical intermediates generated from both anilines and diazomalonates. This reaction could also be extended to other N-heterocycles such as indole and carbazole, and its reaction pathway was validated through electrochemical and photophysical experiments as well as computational studies.
Article
Chemistry, Physical
Quynh H. Nguyen, Ho Seong Hwang, Eun Jin Cho, Seunghoon Shin
Summary: Irradiation of N-enoxybenzotriazoles with blue LEDs in the presence of photosensitizers generates benzotriazolyl and alpha-carbonyl radicals, leading to the synthesis of biologically significant benzotriazolyl derivatives through atom-economic [1,3]-shift and group transfer radical addition reactions.
Article
Chemistry, Physical
Cheol Hyeon Ka, Da Seul Lee, Eun Jin Cho
Summary: This work investigates the solvent-dependent photochemistry of 2-tert-butyl-1,4-benzoquinones and achieves three selective transformations under different solvent conditions.
Review
Chemistry, Multidisciplinary
Da Seul Lee, Vineet Kumar Soni, Eun Jin Cho
Summary: Energy transfer photocatalysis allows direct small-molecule activation and chemical bond formation without sacrificial reagents. Careful selection of substrates and photocatalysts is necessary for selective energy transfer. N-O bond activation generates reactive intermediates for diverse organic transformations. Experimental and computational studies have been performed to support the proposed reaction pathways.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Organic
Seoyeon Kim, Yunjeong Lee, Eun Jin Cho
Summary: In this study, a visible-light-induced selective homocoupling reaction of propargyl bromides to form 1,5-diynes was developed. The key step in the reaction involves the generation of propargyl radicals through a reductive quenching cycle of the photoexcited [Ir(III)]* photocatalyst. The formed 1,5-diyne can be further converted to functionalized indole derivatives through coupling reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shrikant D. Tambe, Eun Jin Cho
Summary: A sustainable photochemical protocol for the oxidation of alcohols to ketones and carboxylic acids was developed using a visible-light organophotocatalyst and molecular oxygen as the oxidant. Superoxide and singlet oxygen were successfully generated through electron transfer and energy transfer pathways, respectively, for the two oxidation steps. Various alcohols were converted into the corresponding ketones or carboxylic acids, and the optimized reaction conditions were applied to the synthesis of benzocoumarin.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Naeem Iqbal, Muhammad Awais Ashraf, Anam Rana Gul, Jaehan Bae, Naila Iqbal, Tae Jung Park, Eun Jin Cho
Summary: We described a new nickel-catalyzed reaction for the synthesis of diversely functionalized pentacyclic benzofurocyclohepta[b]indole derivatives. This unprecedented cascade reaction involves arylative cyclization of alkynes, nucleophilic attack of the indole moiety on the oxonium ion intermediate, 1,2-alkyl group migration, and aromatization. The synthesized molecules showed exceptional cytotoxicity against multiple cancer cell lines while maintaining biocompatibility towards healthy cells.
Article
Chemistry, Multidisciplinary
Cheol Hyeon Ka, Seoyeon Kim, Eun Jin Cho
Summary: Fluoroalkylation is an important synthetic process for modifying molecules with fluoroalkyl groups, which can enhance compound properties and have potential applications in medicine and materials science. The use of visible light-induced, metal-free methods is particularly important due to its environmental friendliness and elimination of potential risks associated with metal-catalyst toxicity. This Account describes our studies on visible light-induced, metal-free fluoroalkylation processes, using organic photocatalysts or EDA complexes. Various pi-systems have been successfully fluoroalkylated under the developed reaction conditions.
Article
Chemistry, Physical
Jaehan Bae, Wooin Lee, Ho Seong Hwang, Seoyeon Kim, Jihee Kang, Naeem Iqbal, Eun Jin Cho
Summary: A novel Ni(II)-catalyzed Meyer-Schuster rearrangement is achieved by utilizing a P-N-type phosphinooxazoline (PHOX) ligand to coordinate with the square planar Ni(II) center. This unconventional transformation allows for the cross-coupling of propargyl acetates with aryl boronic acids to form alpha-arylated enones, without the need for redox additives. Controlled experiments and computational analysis confirm the mechanism involving inner-sphere acyloxy migration.
Article
Chemistry, Physical
Milan Bera, Shrikant D. Tambe, Ho Seong Hwang, Seoyeon Kim, Eun Jin Cho
Summary: We report a regio- and stereoselective synthesis of tetra-substituted olefins via Ni-catalyzed hydroacylation, which shows the opposite regioselectivity to Cu chemistry and is supported by experimental and computational mechanistic studies.
Article
Chemistry, Multidisciplinary
Da Seul Lee, Vineet Kumar Soni, Seunga Heo, Ho Seong Hwang, Youngmin You, Eun Jin Cho
Summary: A sustainable method has been developed to synthesize highly functionalized CF3-hydroquinone derivatives, which exhibit potent biological activity. The approach involves photoirradiation of a mixture containing readily available benzoquinones and CF3SO2Na, resulting in the generation of CF3-hydroquinones through photoinduced charge-transfer reactions. This method is practical, atom-economical, and enables site-selective three-component trifluoromethylation in the presence of vinyl arenes.
Article
Chemistry, Multidisciplinary
Jaehan Bae, Naeem Iqbal, Ho Seong Hwang, Eun Jin Cho
Summary: Efficient and sustainable synthesis of photoactive tetracyclic molecules and their potential as organophotocatalysts are demonstrated in this study, showing promising applications in sustainable photochemical reactions.
