Article
Chemistry, Applied
Vinita Yadav, Ekambaram Balaraman, Santosh B. Mhaske
Summary: This study reports an air-stable, molecularly defined NNN-Mn(II) pincer complex catalyzing acceptorless dehydrogenative coupling of alcohols with indoles, successfully synthesizing various bis(indolyl)methane derivatives and important structurally relevant products. Mechanistic studies highlight the significance of the NH moiety in the complex and the crucial role of metal-ligand cooperation during catalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Mitsuki Onoda, Ken-ichi Fujita
Summary: Esters and ethers are commonly used compounds in modern organic synthesis. The dehydrogenative coupling of primary alcohols for ester synthesis has recently been proposed as an environmentally friendly process. In this study, a new catalytic function switching system was successfully developed using a single iridium catalyst, enabling both dehydrogenative esterification and dehydrative etherification under environmentally friendly conditions.
Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: This article investigates the catalytic performance of iridium complexes in the dehydrogenation of formic acid and examines the effect of auxiliary ligands on the catalytic performance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Sabina Yashmin, Rashid Ali, Santa Mondal, Abu Taleb Khan
Summary: An unprecedented metal-free and catalyst-free synthesis method for synthesizing benzo[c]chromeno[4,3,2-gh]phenanthridine derivatives is reported for the first time. The remote cyclization and aromatization reactions are achieved through a series of reaction steps. A DMSO-assisted synthesis method is also disclosed for the first time.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Alaa A. Atia, Masanari Kimura
Summary: A novel method has been developed for the preparation of 3-allyl-2,3-dihydro-2,3'-bisindoles via homocoupling of N-H indole. The method offers an efficient route to synthesize pharmaceutically active compounds using 3-(indolin-2-yl)-1H-indole derivatives as intermediates.
Article
Nanoscience & Nanotechnology
Krisangi Bordoloi, Gauravjyoti D. Kalita, Pankaj Das
Summary: In this study, a nanostructured iridium catalyst supported on NiO (IrNP@NiO) was introduced for acceptorless dehydrogenative oxidation of primary alcohols. The catalyst was synthesized using a simple wet chemical technique and characterized by various analyses. The catalyst showed high selectivity in converting primary alcohols to acids or carboxylates under the presence of a base, and aldehydes were obtained under base-free conditions. The catalyst also demonstrated efficient conversion of biomass-based alcohols, and could be easily separated and reused multiple times.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Physical
Soumik Biswas, Michael J. Blessent, Benjamin M. Gordon, Tian Zhou, Santanu Malakar, David Y. Wang, Karsten Krogh-Jespersen, Alan S. Goldman
Summary: The PCP-pincer iridium complexes exhibit high regioselectivity for the transfer dehydrogenation of n-alkanes, while the closely related PCOP and POCOP complexes do not. The difference in regioselectivity is a true kinetic phenomenon, not a result of isomerization subsequent to the formation of free alpha-olefin. The different regioselectivity of the POCOPIr vs PCPIr catalysts is attributable to the different rate-determining steps of their respective catalytic cycles, which can be explained in terms of different electronic effects of O versus CH2 linker exerted through the pincer aromatic ring.
Article
Chemistry, Applied
Zhen Deng, Liu-Yan Qiu, Jie Chen, Hui Zhang, Weiguo Cao, Xiao-Jun Tang
Summary: The Cu-mediated N-H trifluoroethylation of NH-containing heteroaromatic compounds with CF3CHCl2 (HCFC-123) has been achieved, which is commercially available in industrial scale. This method is applicable to various NH-containing heteroaromatic compounds, including indoles, pyrroles, pyrazoles, and carbazoles. Moreover, this protocol enables the late-stage trifluoroethylation of NH-containing heteroaromatic bioactive molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Jin-Chen Li, Bing-Xia Yan, Gang Wang, Zhi-Shi Ye
Summary: Here, we demonstrated an efficient cascade reaction of N-tosyl ortho-alkynylanilines and N-acyl ortho-alkynylanilines using Rh(COD)(2)BF4/( t )BuXantPhos as a catalyst. The reaction exhibited excellent chemoselectivity and regioselectivity, high atom-economy, and wide substrate scope. Mechanistic studies revealed that the success of this reaction relied on the strong capability of the rhodium catalyst to recognize the N-substituent group in the selective nucleophilic cyclization and alkyne insertion.
Article
Chemistry, Multidisciplinary
Rushil Fernandes, Krishna Mhaske, Reena Balhara, Garima Jindal, Rishikesh Narayan
Summary: Heterobiaryls are important structural motifs in various fields, and the cross-dehydrogenative coupling is actively explored as a greener alternative for their synthesis. A Cu(I)-catalyzed cross-dehydrogenative coupling of indoles and furans using air as oxidant is reported here, showing high selectivity and good yields with broad substrate scope.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Physical
Sihang Cheng, Zhongling Lang, Jing Du, Zhilu Du, Yingqi Li, Huaqiao Tan, Yangguang Li
Summary: In this study, a new series of tetrahydroquinoxaline-dioximino iridium complexes were designed and investigated, which showed improved hydrogen evolution performance of formic acid and revealed a possible dehydrogenation mechanism. These findings lay the foundation for the implementation of a green hydrogen economy.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Hong Liu, Wan-Hui Wang, Huatian Xiong, A. Nijamudheen, Mehmed Z. Ertem, Mei Wang, Lele Duan
Summary: This study presents a series of Cp*Ir complexes with a rigid 8-aminoquinoline sulfonamide moiety as highly efficient catalysts for the dehydrogenation of formic acid. The electron-donating and electron-withdrawing groups on the ligands were found to have different effects on the reaction steps, leading to lower optimum pH for catalytic activity with electron-withdrawing groups. Overall, this research provides important insights for catalyst design in organic chemistry.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shan Yang, Chenyang Dai, Yujie Chen, Yaqiqi Jiang, Sai Shu, Zhibin Huang, Yingsheng Zhao
Summary: This study presents a direct method for synthesizing 2-phenylacetophenone in moderate to good yields through a ruthenium(II)-catalyzed cross-coupling reaction between acyl and benzyl radicals. The reactions offer a straightforward pathway for synthesizing a variety of ketones with different functional groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Urology & Nephrology
Susana Garcia-Abellan, Vincenzo Passarelli, Manuel Iglesias
Summary: Two Ir complexes, 2a and 2b, with the ligand [Ir(CI)(COD)(NHC)] (COD=1,5-cyclooctadiene), were synthesized through transmetallation from NHC-Ag complexes. Analogously, another Rh complex, 4, was prepared using the same method. By transmetallation from the deprotonated NHC-Ag complex, another Ir complex, 3c, with the ligand [Ir({kappa-C,N-(NHC-acetamide-1H)}(COD)], was synthesized. Similarly, [Ir(CI)(CO)(2)(NHC)] (6) and [Ir({kappa-C,N-(NHC-acetamide-1H)}(CO)(2)] (7) were obtained through carbonylation of 2b and 3c respectively. The catalytic activity of these complexes in formic acid dehydrogenation was evaluated, with the highest turnover frequency (TOF) observed in the presence of a 5:2 HCOOH/Et3N mixture. Stoichiometric experiments suggested COD hydrogenation as the preactivation step.
Article
Biochemistry & Molecular Biology
Asma Hrizi, Manon Cailler, Moufida Romdhani-Younes, Yvan Carcenac, Jerome Thibonnet
Summary: This study describes a method for the preparation of polysubstituted indole-2-carbonitriles through a cross-coupling reaction. The reactivity of indole derivatives with iodine at position 3 was studied using various cross-coupling reactions. Sonogashira, Suzuki-Miyaura, Stille, and Heck cross-couplings provided a variety of di-, tri- and tetra-substituted indole-2-carbonitriles.
Article
Chemistry, Organic
Kun Wang, Saisai Niu, Xin Guo, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: This research discovers a new method to convert prochiral racemic allylic alcohols to enantioenriched chiral alcohols bearing adjacent stereocenters using a diamine diphosphine Ru complex and tBuOK catalyst. The protocol exhibits a wide substrate scope and high selectivities, and can be applied to the synthesis of enantioenriched chromane and indane compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xiaohui Zhang, Wei Ma, Jinyu Zhang, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: The asymmetric hydroalkylation of racemic allylic alcohols has been developed for the synthesis of chiral amino acid derivatives with two remote chiral centers by borrowing hydrogen catalysis. The stereoselectivities are controlled by a single chiral Ru catalyst via a dynamic kinetic asymmetric transformation process and an interesting diastereoselectivity amplification process of the product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yonggang Yan, Jinjin Sun, Gang Li, Liu Yang, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A light-promoted Ni-catalyzed cyanation reaction using 1,4-dicyanobenzene as a cyanating agent is described. Various aryl bromides, chlorides, and druglike molecules are converted to their corresponding nitriles (65 examples). Mechanistic studies reveal that under irradiation, the Ni(II)(dtbbpy)(p-C6H4CN)(CN) oxidative addition product undergoes homolytic cleavage of the Ni-aryl bond to generate an aryl radical and a Ni(I)-CN species, which initiates subsequent cyanation reactions.
Article
Chemistry, Multidisciplinary
Xiaoyun Wu, Wei Ma, Weijun Tang, Dong Xue, Jianliang Xiao, Chao Wang
Summary: A Fe-catalyzed amidation of allylic alcohols with chiral tert-butylsulfinamide has been developed for the synthesis of chiral sulfinamide olefin derivatives. The reaction proceeds under mild conditions with water as the only by-product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Geyang Song, Ding-Zhan Nong, Jing-Sheng Li, Gang Li, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: The Buchwald-Hartwig C-N coupling reaction is widely used in medicinal chemistry. Ni-based catalysts have attracted great attention due to their lower cost and higher reactivity towards less reactive aryl chlorides. However, there is currently no universal Ni catalytic system available for the coupling of electron-rich and electron-poor aryl halides with primary and secondary alkyl amines. In this study, a Ni(II)-bipyridine complex is reported to catalyze efficient C-N coupling of aryl chlorides and bromides with various primary and secondary alkyl amines under direct excitation with light. The feasibility and applicability of this protocol in organic synthesis are demonstrated with over 200 examples.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuxuan Liu, Qi Luo, Qian Qiang, Hua Wang, Yangming Ding, Chao Wang, Jianliang Xiao, Changzhi Li, Tao Zhang
Summary: The sustainable synthesis of quinoxaline derivatives from lignin beta-O-4 model compounds under transition-metal-free conditions has been achieved for the first time in this study. Mechanistic studies showed that this transformation involves highly coupled cascade steps. With this method, a wide range of functionalized quinoxalines, including an important drug compound, were successfully synthesized, demonstrating the potential application of lignin in pharmaceutical synthesis.
Article
Chemistry, Organic
Liu Yang, Yonggang Yan, Ni Cao, Jing Hao, Gang Li, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A highly efficient hydroxylation of (hetero)aryl halides using water as a hydroxyl source via Ni catalysis promoted by PhSiH3 under thermal catalysis is described. This methodology provides a general procedure for the synthesis of diverse multifunctional pharmaceutically phenols and polyphenols, some of which are challenging to be synthesized using literature methods. Mechanism studies reveal that the addition of PhSiH3 leads to the generation of active Ni(I) species, which catalyze the hydroxylation through a Ni(I)-Ni(III) pathway.
Article
Chemistry, Physical
Geyang Song, Ding-Zhan Nong, Qi Li, Yonggang Yan, Gang Li, Juan Fan, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This study demonstrates an easy, efficient, and economic method for synthesizing anilines. By directly exciting light, the amination of aryl halides with ammonium salts can be catalyzed using a Ni(OAc)2-bipyridine complex, allowing a broad range of aryl chlorides and bromides to be converted into primary (hetero)arylamines without the need for an external photosensitizer. The photoinduced generation of Ni(I)-bipyridine species is believed to play a key role in this catalytic cycle.
Article
Chemistry, Multidisciplinary
Wang Miao, Jinyu Zhang, Yanyan Yang, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: The transformation of alcohols into value-added products is of great importance, and this study achieved the selective functionalization of a sp(3) C-H bond on the alkyl side chain of an alcohol, expanding the chemical space of alcohols using the borrowing hydrogen strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuan Gao, Zhijun Wang, Xinyu Zhang, Min Zhao, Shuai Zhang, Chao Wang, Liang Xu, Pengfei Li
Summary: In this study, novel chiral half-sandwich iridium catalysts were designed and synthesized, which enabled the preparation of a broad range of α-chiral (hetero)aryl amines with high yield and enantioselectivity. The optimized catalyst and azeotropic mixture of formic acid and triethylamine were used as the hydrogen source under mild and operationally simple conditions. This work introduced an effective chiral catalyst for the simplified synthesis of medicinally important chiral amines, and also provided a rare example of robust enantioselective transition-metal catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Geyang Song, Qi Li, Ding-Zhan Nong, Jiameng Song, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This paper describes a photochemical C-N coupling reaction of less reactive aryl chlorides with primary and secondary amides using a Ni catalyst without an external photocatalyst. The reaction proceeds under light irradiation (390-395 nm) with a soluble organic amine as the base, resulting in the successful synthesis of a wide range of N-aryl amides from (hetero)aryl chlorides. Mechanistic studies suggest that the amidation occurs via a Ni(I)-Ni(III) catalytic cycle.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Fei Li, Weikang Xiong, Geyang Song, Yonggang Yan, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A general and efficient photochemical C-N coupling method for (hetero)aryl chlorides with hydrazides is presented. The reaction is catalyzed by a Ni(II)-bipyridine complex and does not require an external photosensitizer, making it highly practical. This method demonstrates a wide substrate scope (54 examples) and excellent functional group tolerance, and has been successfully applied to the synthesis of rizatriptan.
Article
Chemistry, Multidisciplinary
Yonggang Yan, Gang Li, Jiani Ma, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This paper reports the photoinduced generation of highly reactive ketyl radicals and their application in C-C coupling, without the need for any external photocatalyst.
Article
Chemistry, Multidisciplinary
Suya Cui, Xiaoyun Wu, Wei Ma, Weijun Tang, Huaming Sun, Jianliang Xiao, Dong Xue, Chao Wang
Summary: An iron-catalyzed coupling reaction between fl-amino alcohols and allylic alcohols for the synthesis of 3,4-dihydro-2H-pyrrole derivatives has been developed. Mechanistic studies suggest that the reaction involves iron-catalyzed dehydrogenative coupling and C-C bond cleavage processes.
GREEN SYNTHESIS AND CATALYSIS
(2021)
Article
Chemistry, Organic
Jennifer Smith, Aysecik Kacmaz, Chao Wang, Barbara Villa-Marcos, Jianliang Xiao
Summary: A series of chiral cyclometalated iridium complexes were synthesized and studied for asymmetric transfer hydrogenation reactions using formic acid as the hydrogen source, showing different activities and enantioselectivities, with the most effective ones achieving up to 63% ee in asymmetric reductive amination of ketones and 77% ee in reduction of pyridinium ions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)