Article
Chemistry, Multidisciplinary
Guilherme L. Tripodi, Magda M. J. Dekker, Jana Roithova, Lawrence Que
Summary: Reactivity of non-heme iron(IV)-oxo complexes is mainly controlled by the ligands, with complexes featuring tetradentate ligands showing the highest reactivity. Fine-tuning of the reactivity of these complexes can be achieved by attaching additional ligands in solution, with the ArIO oxidant playing a previously unknown role. The reactivity of the complexes correlates with the Fe=O and FeO-H stretching vibrations, with the most reactive complex in the series having the weakest Fe=O bond and forming the strongest FeO-H bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Correction
Chemistry, Organic
Mu-Xue He, Yan Yao, Chun-Zhi Ai, Zu-Yu Mo, Yu-Zheng Wu, Qi Zhou, Ying-Ming Pan, Hai-Tao Tang
Summary: This paper examines the electrochemically-mediated C-H functionalization method for constructing tetrasubstituted furan compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Chunyu Han, Yaowen Liu, Xianhai Tian, Frank Rominger, A. Stephen K. Hashmi
Summary: A dual gold/silver-catalyzed cascade reaction was described for the synthesis of indolizines, yielding compounds with diverse functionalities in good to excellent yield. Furthermore, a gram-scale reaction was efficiently conducted in this study.
Article
Chemistry, Organic
Shashikant Tiwari, Diwan S. Rawat
Summary: A novel metal and additive free, atom-economic method for the regiodivergent synthesis of crucial 6- or 8-substituted indolizine from meta-amide-substituted pyridine and alkyne via a [2+2+1] cycloaddition is developed. The reaction proceeds through the cleavage of the carbon-carbon triple bond. The synthesized product contains an important amide group that can be further functionalized to afford biologically active compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lanjun Su, Huan Sun, Jikai Liu, Chengming Wang
Summary: A quaternary carbon center with an oxindole motif was constructed via NHC-catalyzed transition-metal and aldehyde-free intermolecular Heck-type alkyl radical addition. The redox-neutral protocol offers a simple procedure, broad substrate scope, good functional group tolerance, and scalability to gram scale, with a mechanism involving two sets of SET processes and an NHC radical cation intermediate.
Article
Chemistry, Organic
Kai-Xiang Feng, Cheng-Ke Tang, Qiao-Yu Shen, Ai-Bao Xia, Li-Sha Huang, Zhan-Yu Zhou, Xing Zhang, Xiao-Hua Du, Dan-Qian Xu
Summary: The catalytic diastereo- and enantioselective syntheses of C-2-symmetric axially chiral 1,4-dicarbonyl derivatives with 2,3-quaternary stereocenters were successfully achieved utilizing an organo-/iodine binary catalytic strategy. The reactions proceeded well under mild conditions without metals or strong bases.
Article
Chemistry, Physical
Manikantha Maraswami, Hajime Hirao, Teck-Peng Loh
Summary: This study achieved meta-arylation of phenols through copper catalysis with complete meta-selectivity and good tolerance towards various functional groups. Computational studies revealed that the reaction proceeded via a Heck-like pathway.
Article
Chemistry, Applied
Peng Qian, Siqi Jiang, Wenbao Zhang, Hui Zhang, Yuhan Ma, Na Li, Liangquan Sheng
Summary: An electrochemical method was developed for the C(sp(2))-H thiocyanation of pyrazol-5-amines and enamines in an undivided cell. Thiocyanate salts were used as electrolyte and thiocyanating reagent, leading to the synthesis of various thiocyanated derivatives in yields of 36-91%. This protocol was also applicable to the synthesis of iodinated and brominated pyrazol-5-amine derivatives in yields of 51-95%, without the need for a metal or external chemical oxidants and tolerating unprotected amino groups.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Alen Bjelopetrovic, Dajana Barisic, Marina Juribasic Kulcsar, Ivan Halasz, Manda Curic, Stipe Lukin
Summary: We report the mechanochemically-induced deuteration of aromatic C(sp(2))-H bonds activated by Pd at ambient temperature without the need for solvents. Deuterium was sourced from cysteine-d(4) to obtain mono- or dideuterated products from different aromatic palladacycles. Besides the high deuteration yields, we provide a detailed view of the reaction course in the solid state through time-resolved in situ Raman monitoring and DFT calculations. The obtained knowledge could lead to the broader application of this methodology for the deuteration of organic compounds.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Materials Science, Multidisciplinary
Yu Zhang, Liang Zhao, Jianwei Wei, Guanfeng Ji, Huali Wang, Cheng He, Lehua Zhao, Chunying Duan
Summary: This study presents a new Ce-III-based octahedral cage that enhances C(sp(3))-H photoactivation by combining a Ce-IV-Cl photocatalyst and a photoredox catalyst. It integrates photoinduced electron transfer, ligand-to-metal charge transfer, and hydrogen-atom transfer through multiphoton excitation. The cage binds to 2-chloro-9H-thioxanthen-9-one, boosting PET and enabling the oxidation of Ce-III-Cl to Ce-IV-Cl, resulting in the formation of highly electrophilic radicals similar to enzymes.
ACS MATERIALS LETTERS
(2023)
Article
Thermodynamics
Qi Wang, Jacob C. Saldinger, Paolo Elvati, Angela Violi
Summary: The authors developed an atomistic code, SNapS2, to model the formation of PACs in combustion conditions and compared the results with experimental data, demonstrating the unique capabilities of the model in capturing the structures and chemical pathways of PACs.
PROCEEDINGS OF THE COMBUSTION INSTITUTE
(2021)
Article
Chemistry, Multidisciplinary
Xue Feng, Jiaxin Tian, Ying Sun, Huayou Hu, Mingzhu Lu, Yuhe Kan, Danjun Fang, Chao Wang
Summary: The study reports a rhodium-catalyzed directing group promoted selective C-H olefination reaction of indolizines at the 8-position, as well as di-olefination at 2,8-positions achieved with silver hexafluoroantimonate as an additive under similar reaction conditions. Weakly coordinating groups, such as ketone, aldehyde, amide, and ester, were used as directing groups, with the ester group being able to be removed under acid conditions and used as a traceless directing group.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Isaac Choi, Michael J. Trenerry, Ken S. Lee, Nicholas King, John F. Berry, Jennifer M. Schomaker
Summary: In this study, an electrochemically tunable method was developed to achieve the divergent formation of cyclic amines or imines by applying different reaction potentials. Detailed experiments and analysis were conducted to provide mechanistic insight and evaluate atom economy. The method enables selective C-H amidation and imidation reactions, yielding sulfonamide motifs for late-stage modifications.
Article
Chemistry, Multidisciplinary
Bowen Hu, Haoqiang Zhao, Yu Wu, Patrick J. Walsh
Summary: A novel, selective and high-yielding palladium-catalyzed carbonylative arylation of weakly acidic benzylic and heterobenzylic C(sp(3))-H bonds with aryl bromides has been achieved. The system allows access to diverse alpha-aryl or alpha,alpha-diaryl ketones, which are commonly found in biologically active compounds. The use of Josiphos SL-J001-1-based palladium catalyst enables the carbonylative arylation without the formation of direct coupling byproducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Rodney A. Fernandes, Priyanka Choudhary
Summary: This paper reports a sequential iodination of sulfonamides using inexpensive and milder molecular iodine as the iodinating reagent. The nickel and cobalt-catalyzed reaction results in ortho-iodinated arylsulfonamide products, with the 8-amino-5-iodoquinoline moiety serving as a directing group. This methodology can be extended to the synthesis of various value-added products through coupling reactions.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Dan Liu, Kai Yang, Di Fang, Shi-Jun Li, Yu Lan, Yiyun Chen
Summary: This study reports the first method for generating formyl radicals from alpha-chloro N-methoxyphthalimides, which selectively synthesize aldehydes under mild photoredox conditions. The method exhibits excellent chemoselectivity and regioselectivity for installing aldehydes on various organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kun Liu, Zhe Wang, Augustinus N. Kuenzel, Marcus Layh, Armido Studer
Summary: We report a formal intermolecular beta-C-C bond formation reaction of a broad range of aldehydes and ketones with different allyl electrophiles through cooperative nickel and photoredox catalysis. The transformation features mild conditions, excellent regioselectivity, wide functional group tolerance, and high reaction efficiency. This method provides a facile and regioselective approach to beta-allylation of carbonyl compounds, enabling the preparation of valuable building blocks that are difficult to access using existing methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kangbao Zhong, Shihan Liu, Xiaoqian He, Hao Ni, Wei Lai, Wenting Gong, Chunhui Shan, Zhuang Zhao, Yu Lan, Ruopeng Bai
Summary: This report describes the oxidative cyclopalladation activation of a C =C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway involves an oxidative cyclopalladation to generate a pallada-cyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
CHINESE CHEMICAL LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Yumeng Shuai, Jianzhong Zhao, Renheng Bo, Yu Lan, Zengyao Lv, Yihui Zhang
Summary: Mechanically-guided three-dimensional assembly is a novel method for fabricating micro/nanoscale 3D structures and devices. It utilizes compressive buckling in a patterned high-modulus thin film integrated with a low-modulus elastomer substrate. To address the challenges of highly flexible 3D mesostructures or those with large-area suspended features, a wrinkling-assisted strategy is proposed to facilitate the delamination at desired regions. This strategy involves introducing an assisting layer with a weaker film/assisting-layer interface and utilizing wrinkles in the assisting layer to induce additional driving forces for separation.
JOURNAL OF THE MECHANICS AND PHYSICS OF SOLIDS
(2023)
Article
Chemistry, Organic
Jianguo Hu, Shengchun Wang, Bin Li, Aiwen Lei
Summary: We report a protocol for constructing tetrahydroquinolines from bulk chemicals (alkenes and anilines) induced by K2S2O8. The method exhibits operational simplicity, wide scope, mild conditions, and a transition-metal-free system.
Article
Chemistry, Multidisciplinary
Meng Miao, Lei Zhu, Hong Zhao, Lei Song, Si-Shun Yan, Li-Li Liao, Jian-Heng Ye, Yu Lan, Da-Gang Yu
Summary: Difunctionalizing carboxylation of alkynes with CO2 is a sustainable and important strategy to generate valuable acrylate derivatives from readily available starting materials. This study introduces a visible-light-driven and transition metal-free thio-carboxylation of alkynes with thiophenols and CO2. The use of single-electron activation of CO2 leads to unique beta-carboxylation, followed by efficient cyclizing acylation to obtain important thiochromones. The one-pot method features mild reaction conditions, high selectivity, scalability, and facile derivatization of products to bioactive compounds.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Lei Zeng, Shihan Liu, Yu Lan, Lizhu Gao
Summary: This study reports a catalytic asymmetric inverse-electron-demand oxa-Diels-Alder reaction for the synthesis of enantioenriched six-membered oxygen-containing heterocycles. The reaction between α-bromoacroleins and neutral alkenes is catalyzed by oxazaborolidinium cation 1f, leading to the formation of dihydropyrans with high yields and excellent enantioselectivities. The efficient synthesis of (+)-Centrolobine is demonstrated, highlighting the practical utility of this reaction.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Shugao Zhu, Dan Wang, Shihan Liu, Yufeng Ma, Hong Wang, Yu Lan, Ruopeng Bai, Ruwei Shen
Summary: The Pd-catalyzed reaction of 1-(2-iodophenyl)-3-arylprop-2-yn-1-ones with propargyl sulfonamide produces cyclobuta[b]naphthalen-3(1H)-ones, while the reaction with propargyl ethers affords 11H-benzo[b]fluoren-11-ones as products. Experimental and theoretical studies reveal that the former reaction proceeds through Pd-catalyzed cross-coupling, propargyl-allenyl isomerization, and [2 + 2] cycloaddition, while the latter involves Pd-catalyzed cross-coupling, propargylic Alder-ene-type reaction, and 6 pi-electrocyclization leading to the formation of [4 + 2] cycloadducts. The divergent formation of two types of allenic intermediates depending on propargylic substrates is confirmed and elucidated.
Article
Chemistry, Physical
Xinghua Wang, Kai Yang, Ya-Nan Wang, Shi-Jun Li, Donghui Wei, Yu Lan
Summary: Transition-metal-catalyzed transformation reactions of epoxides provide practical C2 synthons and a feasible strategy for catalyst-controlled divergent conversions. Understanding the crucial factors controlling chemoselectivity is key to rational design. Computational studies reveal that the chemoselective reaction can undergo a retro-[3 + 2] step or a carbonyl migration insertion step, influenced by the energy barriers and metal complexes configurations. These insights are important for understanding chemoselectivity and catalyst-controlled reactions.
Review
Chemistry, Multidisciplinary
Wuyin Wang, Wentao Mo, Zishan Hang, Yueying Huang, Hong Yi, Zhijun Sun, Aiwen Lei
Summary: Transition metal element, copper, plays diverse and pivotal roles in oncology. It acts as constituents of metalloenzymes involved in cellular metabolism, function as signaling molecules to regulate the proliferation and metastasis of tumors, and are integral components of metal-based anticancer drugs. Notably, recent research reveals that excessive copper can also modulate the occurrence of programmed cell death (PCD), known as cuprotosis, in cancer cells.
Review
Chemistry, Multidisciplinary
Li Zeng, Jianxing Wang, Daoxin Wang, Hong Yi, Aiwen Lei
Summary: Organic electrosynthesis using alternating current (AC) is still in its early stages due to the lack of a comprehensive theoretical framework. This article provides an overview of recent advancements in AC-driven organic transformations and explores the differences between DC and AC electrolytic methodologies based on their physical principles. These differences include the prevention of metal catalyst deposition, precise modulation of oxidation and reduction intensities, and mitigation of mass transfer processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Wenqiang Zhou, Song Xi, Haohua Chen, Dan Jiang, Jiao Yang, Shuangwei Liu, Ling He, Hanyue Qiu, Yu Lan, Min Zhang
Summary: Bridged frameworks are important in chemistry and biology, found commonly in pharmaceuticals and natural products. Traditional methods of building these rigid segments at the middle or late stage of synthesis decrease efficiency and specificity. In this study, a novel strategy was used to construct a morphan core equipped with an allene/ketone group through an enantioselective a-allenylation of ketones. The resulting bridged backbone guided the assembly of up to five fusing rings, and the allene and ketone groups allowed precise installation of various functionalities, leading to a concise total synthesis of nine strychnan alkaloids.
Article
Polymer Science
Yu Xia, Fulin Zhou, Wenyan Hao, Shan Tang
Summary: The researchers reported a novel strategy for incorporating cleavable disulfide units into the backbone of polyolefins using commercially available diallyl disulfide (DADS) as a comonomer via metathesis copolymerization. This method allows for the synthesis of copolymers with adjustable disulfide content and excellent thermal processability and degradability.
Article
Chemistry, Multidisciplinary
Jinming Wang, Yichang Liu, Xupeng Zong, Aiwen Lei, Zaicheng Sun
Summary: Photochemistry has become increasingly important in organic synthesis and heterogeneous photocatalysts have advantages over traditional homogeneous photocatalysts in terms of production, separation, catalyst recycling, and stability. In this review, the development and advantages of a heterogeneous catalytic system for C-N bond formation as a typical coupling reaction are summarized. Important heterogeneous photocatalysts such as titanium dioxide, semiconductor quantum dots, covalent organic frameworks, and carbon nitrides are discussed in detail. The combination and electron transfer pathway between heterogeneous catalysts and transition-metal catalysts are the focus of this review. These advances not only apply to C-N coupling, but also extend to other coupling reactions.
Article
Chemistry, Multidisciplinary
Yiran Xu, Shengchun Wang, Zhao Liu, Mian Guo, Aiwen Lei
Summary: A photo/nickel dual-catalyzed defluorinative sulfonylation method has been developed to synthesize gem-difluoro allylsulfones rapidly and reliably. This protocol demonstrates mild conditions and a wide scope, providing a novel strategy for the sulfonyl radical participating in radical defluorinative coupling.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
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, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
