Article
Chemistry, Applied
Liang-Neng Wang, Pan-Ting Tang, Ming Li, Jia-Wei Li, Yue-Jin Liu, Ming-Hua Zeng
Summary: The combination of 1,3-diketone and amino acid ligands is essential for the ruthenium-catalyzed C(sp(2))-H arylation of dialkyl phosphines, providing a direct access to aryl-substituted dialkyl phosphine ligands. Mechanistic studies showed that the 1,3-diketone promoted the process of oxidative addition of a cycloruthenium intermediate, and some modified CyJohnPhos ligands exhibited highly catalytic activity in palladium catalyzed C-N bond formation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Zhiyong Hu, Xiao-Jing Wei, Jens Handelmann, Ann-Katrin Seitz, Ilja Rodstein, Viktoria H. Gessner, Lukas J. Goossen
Summary: By tailoring ylide-functionalized phosphines to fit the requirements of Negishi couplings, the challenges in Ar-H coupling have been overcome and the substrate scope has been expanded. Record-setting activities were achieved in arylations using a cyclohexyl-YPhos ligand, enabling couplings of aryl chlorides with Reformatsky reagents and the synthesis of diversely functionalized arylacetic and arylpropionic acid derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Man Ho Tse, Rong-Lin Zhong, Fuk Yee Kwong
Summary: In this study, a general Pd-catalyzed Miyaura borylation of sterically hindered aryl chlorides was achieved using a tailor-made phosphine ligand. The success of this reaction demonstrated the possibility of coupling highly sterically congested electrophilic partners and showed good functional group compatibility. The ligand-enabled C-B bond formation could provide fundamental knowledge for developing catalyst systems suitable for other highly sterically hindered cross-coupling reactions.
Article
Chemistry, Organic
Cunbo Wei, Lizhu Zhang, Zhonghua Xia
Summary: A gold-catalyzed Heck reaction was developed for the synthesis of stilbenes and bistyryl complexes by cross-coupling aryl and styryl iodides with styrenes. The reaction exhibited good functional-group tolerance and mild conditions, assisted by a hemilabile P,N ligand. The mechanism may involve migratory insertion and beta-hydride elimination steps.
Article
Chemistry, Physical
Zhiqian Yu, Qianhui Liu, Yudong Yang, Jingsong You
Summary: This study demonstrates that phenolic compounds can serve as effective ligands to control the regioselectivity of ortho-C-H arylation reactions, enabling the synthesis of various biaryl phosphines in a streamlined and practical manner. The phosphine ligand library shows great potential in catalytic coupling reactions and exhibits unique chemoselectivity when compared with commercially available classic phosphine ligands.
Article
Chemistry, Physical
Amal Benzai, Fazia Derridj, Henri Doucet, Jean-Francois Soule
Summary: The study reports a Pd- or Ru-catalyzed arylation reaction that allows for the ortho-arylation of the aryl unit of 2-arylpyrazines with high regioselectivity and applicability to various substituted pyrazine compounds. Experimental results demonstrate that even pyrazines with 2,3-diphenyl substitution can yield the desired arylated product.
Article
Chemistry, Multidisciplinary
Wei Sun, Luke Wilding-Steele, Richard C. D. Brown, David C. C. Harrowven
Summary: Benzyloxy iodobenzene ethers can undergo cyclisation to form benzo[c]chromenes under UVC irradiation without the need for reagents or catalysts. The reactions proceed through the generation of triplet aryl cations, 5-exo and 3-exo-cyclisations, and subsequent rearomatisation. This methodology is versatile, convenient, and applicable to various related ring systems.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Keita Anoyama, Gen Onodera, Tsutomu Fukuda, Masanari Kimura
Summary: An iridium-catalyzed ortho-C-H silylation of 2-arylpyridine derivative with hydrosilane by using phosphine-borane ligand has been developed. This reaction yields mono- and disilylated products in 81-99% yields, using various 2-arylpyridines. The length of the linkage between phosphorus and boron is crucial for the reaction to proceed.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Yuanting Huang, Yifan Hu, Yukun Han, Yingcong Ou, Yanping Huo, Xianwei Li, Qian Chen
Summary: A three-component reaction involving arynes, trialkyl phosphites, and halides has been achieved under mild reaction conditions, providing a direct synthetic approach to ortho-halogenated arylphosphonates which can be rapidly converted to diversely ortho-functionalized arylphosphorus compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jairus L. Lamola, Paseka T. Moshapo, Cedric W. Holzapfel, Banothile C. E. Makhubela, Munaka Christopher Maumela
Summary: The study investigates the influence of ligand steric bulk on the Pd-catalyzed borylation of ortho-substituted aryl bromides and chlorides under mild conditions (25 - 80 degrees C). Catalysts derived from the less hindered biaryl phobane[3.3.1] 1 (cone angle = 178.5 degrees) exhibited high efficiency for borylation of various ortho-substituted aryl bromides. Dialkylbiaryl phosphine 5 (cone angle = 181.3 degrees) and biaryl phosphacycle 2 (cone angle = 220.0 degrees) possessed suitable ligand steric bulk for facile Pd-catalyzed borylation of ortho-substituted aryl chlorides.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Mei-Ling Wang, Hui Xu, Han-Yuan Li, Biao Ma, Zhen-Yu Wang, Xing Wang, Hui-Xiong Dai
Summary: The Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is achieved via palladium-catalyzed ligand-promoted C-C bond cleavage, providing good to excellent yields of the alkene product. Further applications in the late-stage olefination of drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By using ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved through sequential ortho-C-H alkylation/ipso-Heck olefination.
Article
Chemistry, Multidisciplinary
Xiaomin Shu, De Zhong, Yanmei Lin, Xiao Qin, Haohua Huo
Summary: We report a general and modular approach for the direct enantioselective alpha-arylation of saturated azacycles and acyclic N-alkyl benzamides via nickel/photoredox dual catalysis. This method requires no oxidants or organometallic reagents, features broad substrate scope and high enantioselectivities, and is applicable to late-stage diversification of medicinally relevant complex molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Raghu N. Dhital, Abhijit Sen, Hao Hu, Rikako Ishii, Takuma Sato, Yoko Yashiroda, Hiromi Kimura, Charles Boone, Minoru Yoshida, Yushi Futamura, Hiroyuki Hirano, Hiroyuki Osada, Daisuke Hashizume, Yasuhiro Uozumi, Yoichi M. A. Yamada
Summary: In this study, a phenylboronic ester-activated aryl iodide-selective Buchwald-Hartwig-type amination was developed. The reaction proceeds smoothly to afford the corresponding amines in high yields in the presence of phenylboronic ester. A wide variety of aryl iodides can be applied, while aryl chlorides and bromides remain intact. The reaction is catalyzed by the phenylboronic ester and shows potential antifungal activity.
Article
Chemistry, Organic
Jixing Lai, Chen Yang, Rene Csuk, Baoan Song, Shengkun Li
Summary: The first palladium-catalyzed asymmetric addition of arylboronic acids to coumarins has been successfully developed, providing a straightforward and asymmetric approach for the synthesis of pharmaceutically important 4-aryl-3,4-dihydrocoumarins. This methodology employs easily accessible and stable ligands, has a broad substrate scope, can be conducted under mild reaction conditions, and allows for the accommodation of electron-withdrawing arylboronic acids.
Article
Chemistry, Multidisciplinary
Chuanyong Wang, Xiaobo Hu, Cheng Xu, Qiangqiang Ge, Qingliang Yang, Jianqi Xiong, Wei-Liang Duan
Summary: A novel nickel-catalyzed enantioselective C(sp(2))-P cross-coupling has been developed for the synthesis of P-stereogenic phosphine oxides. The reaction of racemic secondary phosphine oxides with alkenyl/aryl bromides produces P-stereogenic phosphine oxides with high yields and enantioselectivities. The method shows excellent tolerance towards various functional groups and has been applied for late-stage functionalization and product transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Linwei Huang, Shiqing Huang, Zengyu Zhang, Lei Cao, Xingyu Xu, Xiaoyu Yan
Summary: The mesoionic carbene-stabilized PS+ cation 6 has been synthesized and characterized by single-crystal X-ray diffraction analysis for the first time. Computational investigations reveal the multiple-bond character of the phosphorus-sulfur bond, and preliminary coordination investigation shows kappa 1 ligation with the S atom bonded to Cu(I).
Article
Chemistry, Multidisciplinary
Shiqing Huang, Yedong Wang, Chubin Hu, Xiaoyu Yan
Summary: The computational study demonstrated that the nucleophilic activation of sulfur hexafluoride by N-heterocyclic olefins is both thermodynamically and kinetically favorable under mild conditions. The activation process leads to the formation of sulfur pentafluoride anion, and the energy barrier is linearly related to the HOMO energy of substrates. This finding suggests that compounds with higher energy in HOMO can be more efficient in activating SF6.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Organic
Hongyan Zhao, Linwei Huang, Yedong Wang, Kai Feng, Yunhao Chang, Shiqing Huang, Chenxing Ma, Xiaoyu Yan
Summary: A practicable strategy has been established for a reversible mechanochromic material by interconverting classical/frustrated Brønsted acid-base pairs. The study demonstrated the mechanochromic property of 2,6-bis(4-biphenyl)isonicotinic acid, which showed a significant shift in color and exhibited acidochromic behavior. The formation of acid-base interaction was found to be responsible for the mechanochromic phenomenon.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Analytical
Ke Chen, Yuhui Xiang, Xiaoyu Yan, Zhenghui Li, Rui Qin, Jie Sun
Summary: Stable isotope-assisted metabolomics (SIAM) allows global tracking of isotopic labels in living organisms, but its application in tracking transformation products (TPs) of environmental contaminants is challenging. In this study, a H-2-SIAM pipeline coupled with a flexible algorithm was developed to track TPs of contaminants in the environmental matrix.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shiqing Huang, Yixin Wu, Linwei Huang, Chubin Hu, Xiaoyu Yan
Summary: N-heterocyclic imines are widely used in transition-metal chemistry, main-group chemistry and catalysis due to their enhanced basicity and nucleophilicity. Mesoionic N-heterocyclic imines, which feature more highly ylidic form, are still in its early stage but show potential as luminescent materials.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yedong Wang, Yixin Wu, Chang Liu, Jingli Zhang, Xiaoyu Yan
Summary: In recent years, organic mechanofluorochromism (MFC) materials have gained significant attention in various fields. In this study, a series of MFC materials based on interconversion of classical/frustrated Bronsted pairs with a 2-biarylyl cinchoninic acid skeleton were successfully established. These materials exhibited remarkable features such as high contrast, sensitivity, and responsiveness to external mechanical force stimuli, and their luminescence properties could be easily adjusted by changing the substituents.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Organic
Zhihao Xiang, Shiqing Huang, Liang-Liang Zhao, Zengyu Zhang, Ke Chen, Wanqiang Cao, Keyu Zheng, Xiaoyu Yan
Summary: A novel base-catalyzed H/D exchange reaction method of polychlorinated biphenyls with DMSO d(6)/D2O is disclosed, providing excellent deuterium incorporation with good ortho-selectivity.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Florian F. Mulks, Mohand Melaimi, Xiaoyu Yan, Mu-Hyun Baik, Guy Bertrand
Summary: Using computational methods, the redox potentials of BI-s derived from different types of stable carbenes were assessed, and the key parameters influencing the catalytic cycle were studied. It was found that most carbenes have higher reducing powers than thiazol-2-ylidene 1 and the 1,2,4-triazolylidene 2. The solvent polarity influences the reducing power of BI-s, but the redox potential of the oxidant increases at a greater rate, facilitating the reaction. The cation associated with the base also plays a role, especially in nonpolar solvents, with large and weakly coordinating cations being beneficial. Based on the results, mesoionic carbene 3 and abnormal NHC 4 are suggested as promising candidates for oxidative carbene organocatalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chang Liu, Zengyu Zhang, Liang-Liang Zhao, Guy Bertrand, Xiaoyu Yan
Summary: In this paper, a metal-free method using deprotonated Breslow intermediates derived from mesoionic carbenes (MICs) as super electron donors was described for the coupling reaction of aldehydes with non-activated secondary and primary alkyl halides. This mild coupling reaction has a broad substrate scope and tolerates many functional groups, enabling the synthesis of various simple ketones and bio-active molecules through late-stage functionalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Shiqing Huang, Xiaoyu Yan
Summary: Inspired by successful C-F activation, we propose a rational approach based on two-coordinate borinium for activating CF4. Our DFT calculations show that this approach is both thermodynamically and kinetically favorable.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Analytical
Yiguang Qian, Ziyu Chen, Jiahui Wang, Man Peng, Shenghua Zhang, Xiaoyu Yan, Xiaole Han, Xiaohui Ou, Jie Sun, Siyue Li, Ke Chen
Summary: Stable isotope-assisted metabolomics (SIAM) is a powerful tool for discovering transformation products (TPs) of contaminants. In-house H/D exchange reactions enable direct H-2 labeling to target analytes with favorable reaction conditions, providing cost-effective H-2-labeled contaminants of emerging concern (CECs). This study combines the use of in-house H/D exchange and H-2-SIAM to discover potential TPs of 6PPD and proposes a new strategy for finding TPs of CECs.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Chen-Yuan Li, Zengyu Zhang, Xiaoyu Yan
Summary: This study presents a novel strategy for postmodification of difluoromethyl compounds. Ortho-selective C-H borylation of difluoromethyl arenes is achieved by a cyclometalated mesoionic carbene-Ir complex. The regioselectivity is controlled by a hydrogen bond between CF2H and the boryl group via the outer-sphere direction.
Article
Chemistry, Physical
Supphachok Chanmungkalakul, Shiqing Huang, Xia Wu, Esther Cai Xia Ang, Zi-Qi Yang, Yongxin Li, Xiaoyu Yan, Choon-Hong Tan, Davin Tan, Xiaogang Liu
Summary: In this study, a thorough investigation of the selective N-methylation of N-heterocyclic compounds, mainly quinolines and pyridines, was reported. The reactions exhibited good chemoselectivity and were conducted in a base-free manner using iodomethane as the methylating reagent. Thirteen compounds were synthesized to demonstrate the concept and seven crystal structures were obtained. However, the chemoselectivity failed in the presence of a thiol group, as revealed by detailed quantum chemical calculations.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Zengyu Zhang, Shiqing Huang, Chen-Yuan Li, Liang-Liang Zhao, Wei Liu, Mohand Melaimi, Guy Bertrand, Xiaoyu Yan
Summary: N-Heterocyclic carbene-catalyzed transformations via electron-pair-transfer processes have made significant progress, particularly in the umpolung of aldehydes using Breslow intermediates. This study introduces a new type of mesoionic carbene intermediate with a small singlet/triplet gap, allowing for thermally accessible triplet states and various distal difunctionalizations of aryl aldehydes through biradical processes.
Article
Chemistry, Multidisciplinary
Leiyang Lv, Huijun Qian, Yangyang Ma, Shiqing Huang, Xiaoyu Yan, Zhiping Li
Summary: This study presents a robust Pd/NHC ligand synergistic strategy that achieves exclusive alpha-regioselectivity in the C-F bond functionalization reaction. The method enables the efficient construction of branched mono-defluorinative alkylation products.
