Article
Chemistry, Organic
Deepan Chowdhury, Mainak Koner, Suman Ghosh, Mahiuddin Baidya
Summary: Engaging allenes in transition-metal-catalyzed C-H bond activation is a promising strategy for accessing high-value scaffolds. However, the use of cheap and sustainable ruthenium catalysis in this reaction has been elusive. In this study, we report an unprecedented ruthenium-catalyzed (4 + 2) annulation between aromatic amides and allenylphosphine oxides, resulting in high yields of NH-free isoquinolinones. This simple methodology utilizes weak coordination assistance, exhibits high selectivity, and can be applied to the late-stage functionalization of biologically relevant motifs.
Article
Chemistry, Organic
Somratan Sau, Arghadip Ghosh, Majji Shankar, Manash Protim Gogoi, Akhila Kumar Sahoo
Summary: The study demonstrates a unprecedented thioamide-directed cobalt-catalyzed umpolung annulation reaction for the synthesis of highly substituted 2-amidoindenones. The transformation shows regioselectivity and constructs diverse structures, showcasing broad scope and success on a gram scale.
Article
Chemistry, Multidisciplinary
Yan-Zhen Chen, Jian-Guo Fu, Xiao-Ming Ji, Shu-Sheng Zhang, Chen-Guo Feng
Summary: A new method for traceless directing cross-coupling of unreactive C(sp(3))-H bonds and azole C(sp(2))-H bonds has been described. The success of this cascade process relies on the careful selection of a bulky and electron-rich phosphine ligand, and it offers broad substrate scope, excellent regioselectivity, and good functional group tolerance.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jinlian Wang, Ziwei Luo, Yili Wu, Yihan Tang, Xinkan Yang, Gavin Chit Tsui
Summary: We present a simple method for the allylic difluoromethylation of unactivated alkenes. Unlike previous methods that required prefunctionalized allylic substrates, this reaction uses readily available alkenes under mild conditions. Visible light irradiation with PIDA and the use of copper catalyst effectively diverts the reaction towards allylic difluoromethylation rather than hydrodifluoromethylation.
Article
Chemistry, Organic
Suresh Kumar Yadav, Masilamani Jeganmohan
Summary: A redox-neutral [4 + 2] annulation of N-chlorobenzamides/acrylamides with substituted alkenes using Co(III) catalyst at ambient temperature is demonstrated. The reaction provides pharmaceutically important 3,4-dihydroisoquinolinone derivatives in good yields, preserving the synthetically useful functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shuo-Jie Shen, Zhen Zhang, Yi Gu, Cheng-Hao Gu, Xu Yang, Hua-Jin Xu, Yi Hu
Summary: We have developed a cobalt catalyst that is stable in air and abundant in earth, for a regioselective mono-olefination of arenes directed by urea. This reaction operates under mild conditions, with a high selectivity and yield of up to 90%. Compared to noble-metal-catalyzed reactions, our method offers milder reaction conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Dingyi Wang, Xiangyang Chen, Jonathan J. Wong, Liqun Jin, Mingjie Li, Yue Zhao, K. N. Houk, Zhuangzhi Shi
Summary: This study presents a regioselective C7-H silylation of indole derivatives assisted by strong coordination of the palladium catalyst with a phosphorus directing group. The method allows for the effective synthesis of various C7-silylated indoles with broad functional group compatibility. Additionally, the hypothesis regarding the P(III)-directed C-H metalation event is successfully tested through mechanistic experiments and DFT calculations.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Yana Nikolova, Bibiana Fabri, Pau Moneva Lorente, Alejandro Guarnieri-Ibanez, Adiran de Aguirre, Yoshiki Soda, Gennaro Pescitelli, Francesco Zinna, Celine Besnard, Laure Guenee, Dimitri Moreau, Lorenzo Di Bari, Eric Bakker, Amalia Poblador-Bahamonde, Jerome Lacour
Summary: In this study, chiral quinacridines react multiple times with alpha-diazomalonates under Ru-II and Rh-II catalysis, achieving chemo and regioselective insertions of metal carbenes. This versatile method allows for the introduction of mono- or bis-functionalized malonate derivatives, which can be used to tune optical and chemical properties and for cellular bioimaging.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Liming Zhang, Haoran Xu, Weitao Liu, Chengwen Li, Yilin Zhao, Linhai Yan, Yangping Liu, Xianchao Cheng, Xiao-Song Xue, Guifang Han
Summary: A Cu(I)-catalyzed one-pot protocol utilizing benzyl group as a traceless redox-active hydrogen donor has been successfully developed for the hydro-difluoroalkylation of benzyl-protected acrylamides, leading to difluoropentanedioate compounds in moderate to excellent yields. Mechanistic investigations revealed that the reaction proceeds through the addition of a difluoroalkyl radical to acrylamide, followed by unexpected intramolecular 1,4-hydrogen atom transfer (HAT) and SET oxidation reaction. DFT calculations indicated that the chemoselectivity is controlled by destabilizing steric repulsion, resulting in the switch from 1,4-HAT to 5-exo spirocyclization. This work provides a crucial foundation for the application of 1,4-HAT reaction in theoretical and practical synthesis.
Review
Biochemistry & Molecular Biology
Antonio Zucca, Maria I. Pilo
Summary: Rollover cyclometalation is a unique reaction where a chelated heterocyclic ligand undergoes internal rotation to activate a remote C-H bond, forming a novel cyclometalated complex with unique properties. The rollover ligand, with an uncoordinated donor atom, displays multiple personalities and enables a series of distinct reactions, leading to potential applications in catalysis, organic synthesis, and advanced materials.
Article
Chemistry, Multidisciplinary
Xiao-Tian Feng, Jin-Xiu Ren, Xing Gao, Qiao-Qiao Min, Xingang Zhang
Summary: We developed a new practical and stable difluoroalkylating reagent that can introduce the difluoromethylene group into organic molecules under mild reaction conditions via copper catalysis. The method exhibits high selectivity and efficiency and can be used for the synthesis of various complex analogs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yi-Xin Xu, Yu-Qing Liang, Zhong-Jian Cai, Shun-Jun Ji
Summary: A novel chelation-assisted C-H arylation reaction of benzo[h]quinoline is described in this study. The reaction, using [RuCl2(p-cymene)]2 as the catalyst and cheap and easily accessible arylsulfonyl chlorides as the arylation source, exhibits simple reaction conditions, a broad substrate scope, and good functional group tolerance. The successful application of bioactive-molecule-based sulfonyl chlorides further emphasizes the potential utility and importance of this desulfitative C-H arylation protocol.
Review
Chemistry, Multidisciplinary
Sumit Ghosh, Pranjal Pyne, Anogh Ghosh, Alakananda Hajra
Summary: This review summarizes the recent findings and developments in the ortho C-H functionalization of 2-aryl-2H-indazazoles, highlighting its significance in synthetic organic chemistry.
Article
Chemistry, Organic
Wei-Hao Rao, Qi Li, Li-Li Jiang, Xue-Wan Deng, Pan Xu, Fang-Yuan Chen, Ming Li, Guo-Dong Zou
Summary: The copper-catalyzed intermolecular electrophilic amination of benzamides with O-benzoyl hydroxylamines was successfully achieved with the assistance of an 8-aminoquinolyl group, showing good compatibility with various aryl amides and heteroaryl amides as well as excellent tolerance to different functional groups. The monoaminated product was predominantly obtained under simple reaction conditions, and preliminary mechanistic investigations suggested C-H activation to potentially be the rate-determining step.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shengfei Dai, Ke Yang, Yanqi Luo, Ziyuan Xu, Zhi Li, Zhengyi Li, Bijin Li, Xiaoqiang Sun
Summary: Diverse transformations using Selectfluor as a catalyst have been developed for the synthesis of 2,3-dihydrobenzothiazin-4-ones, benzoisothiazol-3-ones and 2-alkylthiobenzonitriles. The selective cleavage of C-S and C-H bonds can be controlled by different reaction conditions. Notably, this study demonstrates the first example of using Selectfluor as a source to construct 2,3-dihydrobenzothiazin-4-ones.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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)