Article
Chemistry, Multidisciplinary
Sif T. Linde, Vasco Corti, Vibeke H. Lauridsen, Johannes N. Lamhauge, Karl Anker Jorgensen, Nomaan M. Rezayee
Summary: This article presents a method for obtaining a versatile chiral biaryl structure through C-H halogenation reactions using high-valent Pd catalysis and chiral transient directing groups. The method is scalable, moisture and air insensitive, and in some cases, requires low Pd-loadings of only 1 mol%. Chiral mono-brominated, dibrominated, and bromochloro biaryls can be prepared in high yield and excellent stereoselectivity, serving as building blocks for various reactions with orthogonal synthetic handles.
Article
Chemistry, Physical
Guoshuai Li, Yifei Yan, Pengfei Zhang, Xiaohua Xu, Zhong Jin
Summary: A new palladium-catalyzed meta-selective C-H olefination of aromatic carbonyl compounds was achieved by utilizing noncovalent hydrogen-bonding interaction directed by engineered N,N'-substituted ureas, demonstrating site-selective control without the need for prior stoichiometric installation and removal of directing groups.
Article
Chemistry, Multidisciplinary
Kananat Naksomboon, Enrique Gomez-Bengoa, Jaya Mehara, Jana Roithova, Edwin Otten, M. Angeles Fernandez-Ibanez
Summary: Pd-catalyzed C-H functionalization reactions of non-directed substrates have emerged as a promising alternative to the use of directing groups. A new type of S,O-ligand has been found to be highly efficient in promoting Pd-catalyzed C-H olefination reactions of non-directed arenes, although its role in the process was unclear. Through various mechanistic tools, it was discovered that C-H activation is the rate-determining step and the S,O-ligand triggers the formation of more reactive Pd cationic species, explaining the observed acceleration of the reaction. These findings provide important insights into the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
Review
Chemistry, Physical
Yuji Nishii, Masahiro Miura
Summary: Dibenzo-fused five-membered heteroaromatic compounds, such as dibenzofuran, carbazole, and dibenzothiophene, are important structural units in various polycyclic heteroaromatic compounds. The intramolecular C-H/C-H biaryl coupling of diaryl (thio)ethers and amines based on palladium(II) catalysis under oxidative conditions is an effective method for their construction. This mini-review briefly summarizes representative examples of constructing structurally intriguing pi-extended polycyclic heteroaromatics through catalytic coupling reactions.
Article
Chemistry, Multidisciplinary
Princi Gupta, Suchithra Madhavan, Manmohan Kapur
Summary: In this study, a method for distal C-H functionalization of monosubstituted ferrocenes using an easily removable directing group under a Pd-II/ mono-N-protected amino-acid ligand catalytic system is reported. The synthetic protocol allows for the synthesis of ferrocene 1,3-derivatives with broad scope in olefins, by functionalizing ferrocenyl methylamine in moderate to good yields through a highly strained ferrocene appended 12-membered palladacycle intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jitan Zhang, Jiaping Wu, Meihua Xie, Jian Fan, Yehe Wu, Ziyi Guo
Summary: In this study, a Pd(II)-catalyzed atroposelective C-H acyloxylation strategy was developed for the synthesis of biaryl aldehyde atropoisomers. Amino acids were used as the catalytic auxiliary and chiral pool. This strategy demonstrates a broad substrate scope, high yield (<= 90%), and excellent enantioselectivity (<= 99%), providing functionalized aldehydes through direct asymmetric C-H oxidation.
Article
Chemistry, Applied
Balazs L. Toth, Gergo Salyi, Attila Domjan, Orsolya Egyed, Attila Benyei, Zsombor Gonda, Zoltan Novak
Summary: The study reports a stereoselective procedure for direct fluorovinylation of aromatic and heteroaromatic scaffolds utilizing palladium-catalyzed ortho C-H activation reaction of aniline derivatives. The use of non-symmetrical aryl(fluoroalkenyl)-iodonium salts as fluoroalkenylating agents allows mild reaction conditions, and feasibility has been demonstrated through over 50 examples.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Francisco Villalba, Ana C. Albeniz
Summary: The pyridone fragment in the ligand plays a crucial role in the C-H activation step of the oxidative Heck reaction. The presence of bipy-6-OH is required for the alkenylation of low acidity fluoroarenes, while it is detrimental for high acidity fluoroarenes. The use of catalytic amount of sodium molybdate as a base is optimal in all these reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Verena Sukowski, Wen-Liang Jia, Rianne van Diest, Manuela van Borselen, M. Angeles Fernandez-Ibanez
Summary: The study presents the C-H olefination of substituted anisole derivatives using a Pd/S,O-ligand catalyst, allowing for a broad range of substituted aryl ethers with good yields and site selectivities. The methodology is straightforward and can be performed under aerobic conditions.
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
Anton Kudashev, Olivier Baudoin
Summary: A ligand-controlled site-selective C(sp(3))-H arylation of heteroaromatic ketones has been developed using Pd catalysis, with selective reactions occurring at the alpha- or beta-position of the ketone side-chain. Addition of a pyridone ligand enables switching from alpha- to beta-arylation. The alpha-arylation process demonstrates broad scope and high site- and chemoselectivity, while the beta-arylation is more limited, with mechanistic investigations suggesting different pathways for the two processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Jitan Zhang, Jian Fan, Ziyi Guo, Yehe Wu, Jiaping Wu, Meihua Xie
Summary: A concise method for the synthesis of axially chiral biaryl aldehydes has been developed through Pd/amino acid-catalyzed interannular C-H arylation of biaryl aldehydes with aryl iodides. This reaction exhibits excellent enantioselectivity and good tolerance towards functional groups. The scalability and potential utility of this asymmetric catalytic protocol have been highlighted.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Jian Tang, Fengjie Lu, Yujie Geng, Yanxia Liu, Ensheng Zhang
Summary: An efficient and straightforward approach for site-selective functionalization of phenylalanine and phenylalanine-containing peptide has been developed via a Pd-catalyzed tandem reaction. The method allows for dual C-H activation, including C-C coupling with benzoquinone and intramolecular C-N cyclization, providing a rapid and feasible synthetic route to incorporate 4-benzoquinone-indoline fragments into peptides.
Article
Chemistry, Multidisciplinary
Luo-Yan Liu, Zhoulong Fan, Md Emdadul Hoque, Shaoqun Qian, Guangrong Meng, Nikita Chekshin, Keita Tanaka, Jennifer X. X. Qiao, Kap-Sun Yeung, Jin-Quan Yu
Summary: Remote C-H functionalization of heterocyclic biaryls is crucial in synthesis and medicinal chemistry. New catalytic templates have been developed to functionalize the hindered ortho-C-H bonds of heterobiaryls, using directing heteroatom at the meta- or para-positions, with unprecedented site-selectivity. This protocol overcomes steric and electronic effects, allowing olefination of sterically hindered heterobiaryls.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Subhendu Ghosh, Tamanna Khandelia, Pritishree Panigrahi, Raju Mandal, Bhisma K. Patel
Summary: A site-selective non-directed C3-maleimidation of quinoxaline is achieved through Mn-(I)-catalyzed reaction. The electrophilic C3-metalation is preferred over the o-directed strategy, leading to diversely substituted quinoxaline-appended succinimides. The products undergo PIFA-promoted C-(sp(2))-C-(sp(3)) spirocyclization via pi-electrons drifting from aryls and Selectfluor-mediated dehydrogenation of succinimide at room temperature.
Article
Chemistry, Physical
Saghnik Saha, Jayabrata Das, Shaeel Ahmed Al-Thabaiti, Soha M. Albukhari, Qana A. Alsulami, Debabrata Maiti
Summary: Selective remote C-H functionalization of aliphatic chains is of great significance and remains a challenging task. The native functional group assisted C(sp(3))-H activation has emerged as a practical and efficient method for transforming aliphatic compounds. Aliphatic acids and amines have gained attention due to their unique coordination abilities with transition metals. This review summarizes the concepts and applications of remote C(sp(3))-H functionalization in aliphatic systems, providing a comprehensive understanding for beginners and experts.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Nupur Goswami, Soumya Kumar Sinha, Partha Mondal, S. Adhya, Ayan Datta, Debabrata Maiti
Summary: Regioselective and site-selective functionalization of distal C-H bonds has been a challenge due to the impact of covalently attached directing groups. Weak non-covalent interactions have been explored with Ir catalysis, but here we demonstrate a Pd-catalyzed meta-selective C-H functionalization of simple amines using anionic ligand and neutral substrate interactions. The site selectivity is governed by the H-bonding interaction between the anionic donating ligand and neutral motifs.
Review
Chemistry, Physical
Rahul Keshri, Debanjan Rana, Argha Saha, Shaeel Ahmed Al-Thabaiti, Abdulmohsen Ali Alshehri, Salem M. Bawaked, Debabrata Maiti
Summary: Transition-metal-catalyzed C(sp2)-H bond functionalization is a revolutionary strategy for efficient synthesis of complex heterocyclic frameworks. The use of free amine and alcohol as directing groups has shown significant advantages, allowing for the formation of C-C and C-heteroatom bonds and annulation cascades reactions. This review focuses on the utility of aromatic sp2-C-H functionalization directed by free amine and hydroxyl for constructing three to seven-membered N- and O-heterocycles.
Article
Chemistry, Multidisciplinary
Wajid Ali, Argha Saha, Haibo Ge, Debabrata Maiti
Summary: The merger of photocatalysis and transition-metal catalysis has led to the development of a versatile platform for environmentally friendly synthetic methods. By combining photoredox and Pd catalysis, a highly efficient, regioselective, and general meta-oxygenation protocol for various arenes has been developed. This protocol operates through a radical pathway and has been demonstrated to work for different substituted arenes using different substituents.
Article
Chemistry, Applied
Suman Maji, Sukumar Pradhan, Karishma Pidiyara, Siddhartha Maiti, Shaeel A. Al-Thabaiti, Debabrata Maiti
Summary: This work presents a palladium(II)-catalyzed regioselective C8-H olefination of 1-naphthamides. Notably, naphthamide fused lactam 2,3-dihydro-1H-benzo[de]isoquinolin-1-one derivatives were synthesized in a particular class of napthamides. The reaction showed good compatibility with a diverse range of acrylates and styrenes, providing the desired products with high yields and tolerance to various functional groups. The developed strategy was further employed for the synthesis of different drug derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Argha Saha, Chiranjit Sen, Srimanta Guin, Chandan Das, Debajit Maiti, Subhabrata Sen, Debabrata Maiti
Summary: We have developed a photoinduced protocol for the synthesis of pharmaceutically important oxazole molecules using diazo- and nitrile-containing reactants. The process involves the initial photolysis of the diazo compound to afford singlet carbenes, which are tapped by nitriles in a [3+2] cycloaddition fashion to give substituted oxazoles. The protocol is applicable for the synthesis of diverse oxazoles and can be used for drug synthesis and isotope labeling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Chemical
Ehtasimul Hoque, Subhajit Ghosal, Nisha Nagar, Rajendra S. Patil
Summary: The flow behaviour of 4-(Dimethylsilyl) butyl ferrocene-grafted HTPB-based composite propellant and basic aluminized HTPB-based propellant was investigated using shear rheometer. Both propellant compositions exhibited shear thinning behavior. The study also analyzed the curing reaction rate and found that toluene diisocyanate had a higher rate compared to isophorone diisocyanate.
ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING
(2023)
Article
Chemistry, Physical
Nupur Goswami, Nikunj Kumar, Sukdev Bag, Puneet Gupta, Debabrata Maiti
Summary: This study investigates the palladium-catalyzed C(sp(2))-Holefination reaction of 2-arylbenzaldehyde with the aid of a temporary directing group. Computational and experimental methods are used to understand the reaction mechanism and selectivity. The results show that the reaction proceeds in three major steps and the selectivity is determined by the C-H activation step.
Article
Chemistry, Multidisciplinary
Jagrit Grover, Suman Maji, Chitrala Teja, Shaeel A. Al Thabaiti, Mohamed Mokhtar M. Mostafa, Goutam K. Lahiri, Debabrata Maiti
Summary: We have developed a novel Mn-SNS-based catalyst for the indirect hydrogenation of CO2 to methanol via formylation. Our catalyst, based on the stable and inexpensive SNS-type tridentate ligand, showed excellent recyclability and effectiveness in the formylation reaction. Various amines, including primary and secondary amines, worked well under the protocol to provide the desired formylated product in good yields. The formed formylated amines can also be further reduced at higher pressures of hydrogen.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Jagrit Grover, Gaurav Prakash, Chitrala Teja, Goutam Kumar Lahiri, Debabrata Maiti
Summary: C-H thioarylation of hydrocarbon building blocks is a highly desirable synthetic transformation due to its prevalence in pharmaceuticals and organic functional materials. However, current developments rely on peroxide mediated transformations which have drawbacks of harsh reaction conditions and functional group intolerance. This study demonstrates a mild metal-free approach for C(sp(3))-H thioarylation using thioxanthone as a photo-catalyst, showing compatibility with various arenes, unactivated alkanes, and cycloalkanes. Post-synthetic modifications are also demonstrated through cross-coupling reactions and functional group interconversions.
Review
Chemistry, Multidisciplinary
Sayan Roy, Subir Panja, Sumeet Ranjan Sahoo, Sagnik Chatterjee, Debabrata Maiti
Summary: C-H functionalisation involves C-H activation and subsequent transformation, converting carbon-hydrogen bonds into carbon-carbon or carbon-heteroatom bonds. Metal-free approaches have gained attention as an alternative to transition metal-catalysed methods, providing a cost-effective and environmentally friendly way to functionalise C-H bonds.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Trisha Bhattacharya, Supratim Ghosh, Subhabrata Dutta, Srimanta Guin, Animesh Ghosh, Haibo Ge, Raghavan B. Sunoj, Debabrata Maiti
Summary: The significance of stereoselective C-H bond functionalization lies in its direct application potential to pharmaceuticals or complex chiral molecule synthesis. In this work, we harnessed the cooperative ligand approach to control two different stereogenic elements in the same molecule, resulting in the synthesis of axially chiral biaryls.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Uttam Dutta, Gaurav Prakash, Kirti Devi, Kongkona Borah, Xinglong Zhang, Debabrata Maiti
Summary: A method for directing group-assisted para-selective C-H alkynylation using Rh catalyst has been reported. The para-selectivity was achieved with the assistance of a cyano-based directing template, and remained unaltered regardless of the steric and electronic influence of the substituents. The study provides insights into the mechanistic intricacies and shows potential applications for post-synthetic modification.
Review
Chemistry, Multidisciplinary
Soumya Kumar Sinha, Pintu Ghosh, Shubhanshu Jain, Siddhartha Maiti, Shaeel A. Al-Thabati, Abdulmohsen Ali Alshehri, Mohamed Mokhtar, Debabrata Maiti
Summary: C-H activation plays a crucial role in the synthetic strategies for multi-step transformations, but its importance lies in its application in large-scale industrial processes and the synthesis of complex natural products. Recent advancements in C-H activation methodologies have led to the discovery of more efficient synthesis methods and accelerated the synthesis of complex organic compounds.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Uttam Dutta, Gaurav Prakash, Kirti Devi, Kongkona Borah, Xinglong Zhang, Debabrata Maiti
Summary: In this study, the first report on the rhodium-catalyzed para-selective C-H alkynylation is presented, and its mechanistic insights are obtained from experimental and computational studies. The para-selectivity is achieved with the assistance of a cyano-based directing template, which remains unchanged regardless of the steric and electronic influence of the substituents.
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)
