Article
Chemistry, Multidisciplinary
Maximilian Franta, Johannes Gramueller, Philipp Dullinger, Simon Kaltenberger, Dominik Horinek, Ruth M. Gschwind
Summary: Chiral phosphoric acids (CPA) have been widely used as catalysts in organocatalysis, but the selection of the optimal catalyst is still a challenge. This study identified two reaction pathways with inverse stereoselectivities in the CPA-catalyzed transfer hydrogenation of imines, involving either a single CPA or a hydrogen bond bridged dimer as the active catalyst. Through NMR measurements and DFT calculations, it was revealed that the dimeric pathway had stronger substrate activation via cooperativity. The temperature and catalyst loading could be adjusted to favor either pathway and enhance the enantiomeric excess (ee) of the product. This research is expected to have a significant impact on the optimization and prediction of CPA catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Michael A. Stevens, Annie L. Colebatch
Summary: This article examines modes of cooperativity and catalytic mechanisms in metal-metal cooperative catalysts by studying (de)hydrogenation processes and drawing lessons from the development of metal-ligand cooperative catalysts.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Sichan Dong, Xinjun Luan
Summary: The Catellani reaction, discovered by Catellani in 1997 and further developed by Catellani, Lautens, and others, is a powerful strategy for the synthesis of polysubstituted arenes. This method allows for the simultaneous functionalization of both ortho- and ipso-positions of aryl halides with different electrophiles and terminating agents under the cooperative catalysis of palladium and norbornene. The review focuses on the significant progress in such transformations and categorizes typical Catellani reactions into five parts based on the functionalization modes of ortho-C-H bonds: alkylation, arylation, amination, acylation, or thiolation.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Wei Hao, Katherine L. Bay, Caleb F. Harris, Daniel S. King, Ilia A. Guzei, Michael M. Aristov, Zhe Zhuang, R. Erik Plata, David E. Hill, K. N. Houk, John F. Berry, Jin-Quan Yu, Donna G. Blackmond
Summary: This study investigated the influence of chiral monoprotected aminoethyl amine (MPAAM) ligands on enantioselective Pd-catalyzed arylation of strong cyclopropane C(sp(3))-H bonds. The results revealed a subtle impact of ligand structure on reaction kinetics and mechanism, as well as a negative dependence of ligand concentration on reaction rate. These findings demonstrate the importance of ligand design in catalytic reactions.
Article
Chemistry, Organic
Hyeonbin Ha, Ho Jeong Choi, Hahyoun Park, Yunyeong Gwon, Jiin Lee, Jaesung Kwak, Min Kim, Byunghyuck Jung
Summary: The research reveals the use of 3-bromo-2-hydroxybenzaldehyde as a transient directing group in the Pd-catalyzed gamma-position sp(3)-C-H arylation of primary amines, and detailed the reaction mechanism and high selectivity origins through density functional theory calculations and X-ray crystal structure analysis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Rui Liu, Meng-Lan Shen, Lian-Feng Fan, Xiao-Le Zhou, Pu-Sheng Wang, Liu-Zhu Gong
Summary: Allylamines are important for synthesizing bioactive compounds and can be obtained through the palladium-catalyzed allylic C-H amination of 1,4-dienes. This reaction favors the formation of thermodynamically unstable Z-allylamines with aromatic amines. Aliphatic cyclic amines can also participate, but linear dienyl allylic amines are the main products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marti Garcon, Nicolette Wee Mun, Andrew J. P. White, Mark R. Crimmin
Summary: This study demonstrates a new method of transforming C-H bonds into C-Zn bonds using a palladium catalyst and zinc hydride reagent, which has been successfully applied to various types of arenes with high selectivity. Mechanistic studies show that heterometallic complexes play a crucial role in the catalytic process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kaveh Farshadfar, Samaneh K. Tizhoush, Alireza Ariafard
Summary: This study provides a detailed explanation for the observation that Bronsted acids can promote Pd-catalyzed functionalization of C-H bonds. Density functional theory calculations show that the presence of Bronsted acid reduces the energy barrier for C-H activation, leading to accelerated reactions.
Article
Chemistry, Multidisciplinary
Nihad Salameh, Federica Valentini, Olivier Baudoin, Luigi Vaccaro
Summary: We report a general and efficient enantioselective C-H arylation of aryl bromides using BozPhos as the bisphosphine ligand and SP-NHC-PdII as recoverable heterogeneous catalyst. By exploiting the release and catch mechanism of action, high enantioselectivities were achieved across different substrates containing methyl, cyclopropyl and aryl C-H bonds. The developed catalytic system provides a more sustainable solution for the synthesis of high added-value chiral products through recycling of the precious metal.
Article
Chemistry, Multidisciplinary
Barry M. Trost, Zhijun Zuo
Summary: A novel Pd-0-catalyzed highly selective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class of [5,5] spirocyclic carbo- and heterocycles. The regioselectivity of the reaction can be controlled by fine-tuning the Pd-pi-allyl intermediate, with excellent toleration of various coupling partners and enantioselectivities demonstrated through further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Matthew Wheatley, Marco Zuccarello, Maria Tsitopoulou, Stuart A. Macgregor, Olivier Baudoin
Summary: In this study, mechanistic investigations were conducted on the reactivity of various alpha-substituted C(sp(3))-H bonds in the context of Pd-0-catalyzed C(sp(3))-H arylation. The results provide important insights into the reaction kinetics and a reactivity scale was determined, which will be useful for future studies in transition-metal-catalyzed C(sp(3))-H activation.
Article
Multidisciplinary Sciences
Ji-Min Yang, Yu-Kun Lin, Tao Sheng, Liang Hu, Xin-Pei Cai, Jin-Quan Yu
Summary: Regiocontrol is challenging in traditional cycloaddition reactions between unsaturated carbon compounds. This study reports a regio-controllable synthesis of benzocyclobutenes (BCBs) through a palladium-catalyzed double C-H activation of adjacent methylene units in carboxylic acids using bidentate amide-pyridone ligands. This method allows for the synthesis of diversely functionalized BCBs and hetero-BCBs found in drug molecules and bioactive natural products.
Article
Chemistry, Multidisciplinary
Rie Yoshimoto, Attila Taborosi, Qiyuan He, Yusuke Ano, Naoto Chatani, Seiji Mori
Summary: The reaction between aromatic amides and maleimides, catalyzed by palladium, leads to the formation of a product with double C-H bond activation, occurring at both the benzylic and meta positions. Computational chemistry studies reveal a stepwise mechanism involving a six-membered palladacycle, maleimide insertion, protonation of the Pd-N bond, and activation of the meta C-H bond. The site selectivity is determined by the interaction energy controlling the insertion of maleimide into the Pd-C(sp(3)) bond. The meta C-H bond activation step is identified as the rate-determining step based on the energetic span model. The 2-thiomethylphenyl group is found to function effectively as a directing group due to strong Pd-S bonding and the destabilizing effect of the deformation energy.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xin Yu, Lingfei Hu, Wolfgang Frey, Gang Lu, Rene Peters
Summary: Catalytic allylic substitution is an important method in asymmetric synthesis to generate C-C bonds with enantioselectivity. However, a common limitation is the formation of allylic substitution products with (E)-configured C=C double bonds. In this study, a planar chiral palladacycle catalyst was used to achieve a diastereospecific reaction outcome, maintaining the C=C double bond geometry of the allylic substrates in highly enantioenriched products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Alexandra M. Zima, Oleg Y. Lyakin, Anna A. Bryliakova, Dmitrii E. Babushkin, Konstantin P. Bryliakov, Evgenii P. Talsi
Summary: Catalytic approaches to late-stage creation of new C-O bonds, especially via oxygenation of particular C-H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established. In this Personal Account, recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp(3))-H groups are analyzed, with a focus on the factors governing the oxidation chemo- and stereoselectivity.
Article
Chemistry, Physical
Jiandong Guo, Hai D. Pham, Yan-Bo Wu, Dongju Zhang, Xiaotai Wang
Article
Chemistry, Multidisciplinary
Hao Xie, Jiandong Guo, Yu-Quan Wang, Ke Wang, Peng Guo, Pei-Feng Su, Xiaotai Wang, Xing-Zhong Shu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Jiandong Guo, Wu Yang, Dongju Zhang, Shou-Guo Wang, Xiaotai Wang
Summary: This study reveals a plausible mechanism for the formation of all-carbon quaternary stereocenters through the Sc-catalyzed C-H cycloaddition of imidazoles to 1,1-disubstituted alkenes. The Sc complex activates the C2-H bond in the imidazole substrate and undergoes intramolecular cyclization to generate the quaternary center. The findings also highlight the electronic and steric effects on catalyst activity and enantioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Agriculture, Multidisciplinary
Chi-Yuan Cheng, Tatiana Brinzari, Zhigang Hao, Xiaotai Wang, Long Pan
Summary: Amino acids were found to accelerate the hydrolysis of methyl salicylate in an alkaline environment, with glycine playing a crucial role in this process. The presence of an ortho-hydroxyl substituent in methyl salicylate and the carboxyl group of glycine were identified as essential for the hydrolysis of methyl salicylate.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xi Deng, Jiandong Guo, Xiaofeng Zhang, Xiaotai Wang, Weiping Su
Summary: The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B(2)cat(2) has been achieved without additives, covering a broad substrate scope and tolerating diverse functional groups. Experimental and computational studies revealed a detailed mechanism involving a concerted decarbonylation and reductive elimination step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daming Ren, Hai-Lun Xia, Kang Zhou, Shenjie Wu, Xiao-Yuan Liu, Xiaotai Wang, Jing Li
Summary: Research shows that utilizing luminescent metal-organic frameworks (LMOFs) with tunable structures can effectively investigate energy transfer (ET) over the entire visible light range. By successfully installing radiative and derivative dicarboxylic acids into LMOFs matrices, ET can be easily controlled, forming a two-dimensional space for emission tuning.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shenjie Wu, Daming Ren, Kang Zhou, Hai-Lun Xia, Xiao-Yuan Liu, Xiaotai Wang, Jing Li
Summary: By utilizing linker engineering and a mixed-linker strategy, the emission behavior of UiO-68 type metal-organic frameworks can be systematically tuned, leading to significantly enhanced quantum yield and increased lifetime.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Engineering, Chemical
Chi-yuan Cheng, Hongwei Shen, Nan-Nan Shen, Cristina Castro, Viktor Dubovoy, Donghui Wu, Ravi Subramanyan, Xiao-Ying Huang, Chloe E. Pitsch, Xiaotai Wang, Long Pan
Summary: This study reports a novel complex consisting of an ion pair of arginine-arginine carbamate, isolated from an aqueous solution after reacting with CO2. The structure was elucidated through X-ray diffraction, and NMR studies revealed the hydrolysis rate of the complex in aqueous conditions. Density functional theory calculations showed how the amino group acted as a nucleophile to attack CO2, leading to the formation of the ion pair. The discovery expands understanding of CO2 fixation and can potentially lead to new methods for CO2 capture using amino acids.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Chemistry, Physical
Xia Zhao, Dongju Zhang, Xiaotai Wang
Summary: This study investigates the detailed working mechanism of a notable base-free cross-coupling reaction using density functional theory. It reveals that the reaction proceeds through a complex Pd(0)/Pd(II) pathway and elucidates the dual role of an arylboronic acid as a reducing agent and coupling partner. These mechanistic insights have important implications for new reaction development.
Article
Chemistry, Inorganic & Nuclear
Jiandong Guo, Dongju Zhang, Xiaotai Wang
Summary: This study presents a novel hydrodefluorination reaction initiated by nickel hydride HAT, providing mechanistic insights and implications for developing new metal hydride HAT-initiated reactions.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Jian-Hong Bian, Wen-Yan Tong, Chloe E. Pitsch, Yan-Bo Wu, Xiaotai Wang
Summary: A detailed DFT mechanistic study on Ni-catalyzed direct carbonyl-Heck coupling of aryl triflates and aldehydes to form ketones was presented. The study revealed that the triflate anion in the second coordination sphere engages in electrostatic interactions with the first sphere, stabilizing the intermediate/transition state and enabling the desired reactivity.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Xianghua Tao, Yanchi Chen, Jiandong Guo, Xiaotai Wang, Hegui Gong
Summary: This work demonstrates the synthesis of alpha-vinyl and aryl amino acids via Ni-catalyzed cross-electrophile coupling, with experimental and DFT studies showing simultaneous addition of glycine alpha-carbon radicals to Ni(0) and Ar-Ni(ii). The auxiliary chelation of the N-carbonyl oxygen to the Ni center is crucial for stabilizing the Gly-Ni(i) intermediate.
Article
Chemistry, Physical
Jiandong Guo, Dongju Zhang, Xiaotai Wang
Article
Chemistry, Multidisciplinary
Wen-Yan Tong, Thu D. Ly, Tao-Tao Zhao, Yan-Bo Wu, Xiaotai Wang
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Inorganic & Nuclear
Wen-Yan Tong, Tao-Tao Zhao, Xue-Feng Zhao, Xiaotai Wang, Yan-Bo Wu, Caixia Yuan
DALTON TRANSACTIONS
(2019)