Review
Chemistry, Applied
Cairong Wang, Ge Qiu, Chen Li, Kai Sun, Zhichuan Wang, Xin Wang
Summary: Carboxylic acid compounds are important structural units that exist widely in nature, and decarboxylative reactions have great significance in synthetic chemistry due to the non-flammable, non-toxic, and easy-to-remove byproduct carbon dioxide. Heterocyclic compounds are important backbones of various biologically active molecules, making research on new synthetic tactics for heterocyclic derivatives based on decarboxylative cyclization of great interest.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Magdalena Tasic, Albert Ruiz-Soriano, Daniel Strand
Summary: This article describes a practical three-step approach to diareno[a,e]cyclooctatetraenes using an efficient copper(I) catalyzed double decarboxylation as the key step. The method relies on cheap and abundant reagents, can be performed on scale, and is also applicable to unsymmetrical derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ryosuke Yamada, Komei Sakata, Takahiro Yamada
Summary: An efficient method for synthesizing 2,6-multisubstituted morpholines via electrochemical intramolecular etherification has been developed. This method, which is easy to perform and scalable, allows for the production of various substituted morpholine derivatives in high yields. The utility of this method is demonstrated by the synthesis of 2,2,6,6-tetrasubstituted morpholines, which are challenging to efficiently synthesize using previously reported strategies.
Article
Chemistry, Organic
Pidiyara Karishma, Chikkagundagal K. Mahesha, Sanjay K. Mandal, Rajeev Sakhuja
Summary: A mild Rh-catalyzed method was developed for the synthesis of hydroxyimino functionalized indazolo[1,2-a]cinnolines and phthalazino[2,3-a]cinnolines by reductive [4 + 2] annulation between 1-arylindazolones and 2-aryl-2,3-dihydrophthalazine-1,4-diones with varied nitroolefins. The targeted oxime decorated tetracyclic fused cinnolines were synthesized via sequential C-H activation/olefin insertion/reduction under reducing-agent-free conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Bo Yang, Shi-Jun Li, Yongdong Wang, Yu Lan, Shifa Zhu
Summary: Hydrogen atom transfer is an effective strategy for activating C-H bonds and further functionalization. Introducing water as both a hydrogen source and HRS enables internal hydrogen radical transfer, providing a breakthrough in hydrogen radical transfer for challenging processes in organic synthesis.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Caiyun Ou, Yinxia Cai, Yuyang Ma, Haozhen Zhang, Xiaoyu Ma, Chao Liu
Summary: This paper reports a photocatalytic decarboxylative fluorosulfonylation reaction using various hypervalent iodine(III) carboxylates, 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a sulfonyl source, and KHF2 as a fluorine source. The reaction proceeds through a radical sulfur dioxide insertion and fluorination strategy. Additionally, a one-pot photocatalytic decarboxylative fluorosulfonylation reaction of various carboxylic acids mediated by PhI(OAc)(2) was realized, without the need for catalysts.
Article
Chemistry, Multidisciplinary
Sudip Sau, Prasenjit Mal
Summary: The study presents a metal-free one-pot synthesis of 3-nitro-coumarins from aryl alkynoates using tert-butyl nitrite as the sole reagent. The reaction proceeds via radical triggered cyclization and nitration using a cascaded mechanism, showing high efficiency and environmental friendliness.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Emma G. L. Robert, Eliott Le Du, Jerome Waser
Summary: An oxidative-decarboxylative intramolecular cyclisation of dipeptide derivatives has been reported using phenyl iodine(iii) diacetate (PIDA) in combination with BF3 center dot OEt2. This reaction provides access to a variety of valuable polycyclic N-heterocyclic scaffolds containing 5-, 6-, or 7-membered rings.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Han Ding, Ningjie Yan, Peng Wang, Ni Song, Qikai Sun, Tiantian Li, Ming Li
Summary: An efficient protocol for organophotocatalytic synthesis of reverse glycosyl fluorides (RGFs) has been established using 9-mesityl-10-methyl-acridinium (Mes-Acr(+))-mediated oxidative decarboxylative fluorination of uronic acids. Both pentofuranoid and hexopyranoid uronic acids can serve as viable substrates for this transformation, and a wide range of functional groups are tolerated. The potential of this reaction is demonstrated by the convenient synthesis of RGF-type nucleosides, particularly those with a unique l-lyxo-configuration, thereby providing a novel method to expand the chemical space of nucleosides widely used in drug discovery and development.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Seunghwan An, Kwang Ho Song, Sunwoo Lee
Summary: The synthesis of vinyl sulfone derivatives via the reaction of arylpropiolic acids, K2S2O5, and aryl boronic acids using the CuBr2/1,10-phenanthroline catalytic system in the presence of acetic acid provides the desired products in moderate to good yield, showcasing excellent functional group tolerance.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Robin Cauwenbergh, Prakash Kumar Sahoo, Rakesh Maiti, Abra Mathew, Rositha Kuniyil, Shoubhik Das
Summary: Primary aliphatic amines are important compounds, and finding new chemical routes for their synthesis has gained significant interest. The hydroaminoalkylation reaction is desirable due to the availability and lower price of olefins. The decarboxylative radical-polar crossover process can be used to synthesize functionalized linear aliphatic primary amines.
Article
Chemistry, Multidisciplinary
Wei-Feng Zheng, Jingdan Chen, Xiaotian Qi, Zhongxing Huang
Summary: Stereoselective protonation is a challenge in asymmetric catalysis, but it can convert abundant acid feedstocks into structurally diverse chiral molecules. Researchers have demonstrated an anchoring group strategy to create additional catalyst-substrate interactions, allowing enantioselective decarboxylative protonation to produce alpha-amino acids. This malonate-based synthesis introduces side chains and enables the access of structurally and functionally diverse amino acids.
Article
Chemistry, Multidisciplinary
P. Scott Pedersen, David C. Blakemore, Gary M. Chinigo, Thomas Knauber, David W. C. MacMillan
Summary: In this study, a new synthetic method was reported to form sulfonamides, important amide bioisosteres, by coupling carboxylic acids and amines. This method utilizes copper ligand-to-metal charge transfer (LMCT) to convert aromatic acids to sulfonyl chlorides, followed by one-pot amination to form the corresponding sulfonamide. The method can be applied to a diverse set of substrates and also enables the synthesis of (hetero)aryl sulfonyl fluorides, which have utility in chemical probes and programmable bifunctional reagents.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yang Gao, Benxiang Zhang, Laura Levy, Hai-Jun Zhang, Chi He, Phil S. Baran
Summary: This article reports the first enantioselective decarboxylative Negishitype alkylations of alpha-oxy carboxylic acids via the intermediacy of redox-active esters (RAEs). The transformation enables the radical-based retrosynthesis of seemingly trivial enantiopure dialkyl carbinols. The article discusses the history of such couplings, the retrosynthetic ramifications, general conditions development, and showcases various applications that demonstrate its simplification effect on synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yi An, Mengjuan Wu, Weijian Li, Yaling Li, Zhenzhen Wang, Yansong Xue, Pei Tang, Fener Chen
Summary: The work reported a concise and enantioselective total synthesis of the Schizozygine alkaloid (-)-strempeliopine. A synthetic strategy featuring palladium-catalyzed decarboxylative asymmetric allylic alkylation and diastereoselective Bischler-Napieralski/lactamization was developed to construct the pentacyclic core structure with complete control of four neighbouring stereocenters.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ankit Kumar Mittal, Gaurav Prakash, Pramod Pathak, Debabrata Maiti
Summary: This paper presents a safer, scalable, and continuous process for synthesizing picramide. The process consists of two steps: nitration of p-nitroanisole (PNAN) to 2,4,6-trinitrianisole (TNAN) in the first step, and ammonolysis of TNAN to picramide in the second step. Flow optimization resulted in yields of 90% and 98% for step-1 and step-2 respectively, with HPLC purity greater than 99% for the obtained picramide. The flow process offers significant advantages in selectivity and yield compared to the batch process in step-1. The optimized flow process was successfully scaled up to a production rate of 25 g/hr in a laboratory flow reactor, demonstrating its suitability for commercial-scale production of picramide.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
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.
Article
Chemistry, Multidisciplinary
Mohamed Mokhtar, Subir Panja, Abdulmohsen Alshehri, Wael Halawani, Debabrata Maiti
Summary: A nanocomposite catalyst based on CuO/ZnO/ZrO2 materials was developed using the coprecipitation method and subsequent calcination. The catalysts were characterized using TGA, XRD, SEM, and N-2-physisorption analysis. The nanocomposite catalyst with a Cu/Zn ratio of 1:1 exhibited the smallest particle size and largest surface area. It demonstrated excellent efficacy for the oxidation of benzylic alcohol under optimal conditions and could be used for up to three catalytic cycles with minimal loss of activity.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Prabhat Kumar Baroliya, Mukesh Dhaker, Subir Panja, Shaeel Ahmed Al-Thabaiti, Soha M. Albukhari, Qana A. Alsulami, Arnab Dutta, Debabrata Maiti
Summary: Electrochemically promoted transition metal-catalyzed C-H functionalization is a promising area of research, but it is still at an early stage compared to traditional chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically promoted metal-catalyzed C-H functionalization. From the perspective of sustainability and cost effectiveness, electrochemically promoted oxidation of a metal catalyst offers a mild, efficient, and atom-economical alternative to traditional chemical oxidants. This Review discusses advances in the field of transition metal-electrocatalyzed C-H functionalization and how electricity enables metal-catalyzed C-H functionalization in an economic and sustainable way.
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, Applied
Ankit Kumar Mittal, Gaurav Prakash, Pramod Pathak, Bishal Dutta, Nandita Ahalyan, Siddhartha Maiti, Debabrata Maiti
Summary: Here, we present a flow chemistry method for synthesizing tert-butyl nitrite with a high yield of 95% and a short residence time of 1min, corresponding to a space time yield of 13 g/h/mL. In addition, we demonstrate the application of tert-butyl nitrite in metal-free stereoselective nitration of alkenes. The traditional batch process, with a cycle time of 12 to 24 h, is limited for commercial production. Therefore, we developed a continuous-flow nitration process using a fixed bed column reactor, reducing the reaction time from 12 h to 3 min and achieving a faster and more efficient synthesis.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(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.
Review
Chemistry, Physical
Tapas Kumar Achar, Shaeel Ahmed Al-Thabaiti, Mohamed Mokhtar, Debabrata Maiti
Summary: Chiral poly(hetero)cyclic compounds are commonly found in bioactive molecules, natural products, and functional materials. The synthesis of these compounds typically involves tedious classical synthetic procedures. However, recent advancements in transition-metal-catalyzed C-H bond activation and cyclization reactions have provided a more efficient approach. Despite these advancements, the synthesis of chiral annulated products remains challenging. This review highlights recent advancements in asymmetric annulation reactions catalyzed by chiral CpxM(III) complexes, focusing on the mechanistic understanding of the developed protocols.
Article
Chemistry, Multidisciplinary
Debajit Maiti, Argha Saha, Srimanta Guin, Debabrata Maiti, Subhabrata Sen
Summary: In this study, a reagent-less electro-photochemical reaction using electricity and blue LED was developed for the synthesis of diverse substituted oxazoles, diastereo-selective imide-fused pyrroles, and tetrahydroepoxy-pyridines. Mechanistic investigation confirmed the formation of carbene radical anions. The reaction has significant implications for the synthesis of important heterocycles.
Article
Chemistry, Multidisciplinary
Angus Olding, Curtis C. Ho, Debabrata Maiti, Alex C. Bissember
Summary: This article explores a series of case studies that examine key strategies enabling the structural authentication of important species in palladium- and nickel-catalysed C-C, C-N, and C-O cross-coupling reactions. It focuses on studies confirming the structures of challenging intermediates using X-ray crystallography, while providing mechanistic insights from these reports.
CHEMICAL COMMUNICATIONS
(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
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)
