Review
Chemistry, Multidisciplinary
Yan-Long Zheng, Stephen G. Newman
Summary: This article discusses two common families of chemical reactions - cross-coupling reactions and pi bond addition reactions - and the significant overlap between them. Recent advancements in catalysis have revealed the role of compounds such as esters, aldehydes, and alcohols in nickel- and palladium-catalyzed reactions, offering promising alternatives for the preparation of amides, ketones, substituted alcohols, alkanes, and more. The focus is on the key mechanistic steps that allow these non-traditional substrates to be incorporated into cross-coupling-like catalytic cycles.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Physical
Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: This paper summarizes our team's efforts over the past two decades in the development of new catalytic methods for C-C bond formation. The versatile applications of the commercially available catalyst RuHCl(CO)(PPh3)(3) (or RuH for short) are highlighted through eight different transformations. The fundamental steps involved in the catalysis are emphasized, demonstrating how our mechanistic understanding and the diverse catalytic capabilities of RuH can be utilized to design desired catalytic cycles and develop new cross-coupling reactions with high atom-economy.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Physical
Guang-Yan Xing, Ya-Cheng Zhu, Deng-Yuan Li, Pei-Nian Liu
Summary: On-surface synthesis, a powerful tool for atomically precise fabrication of low-dimensional carbon nanomaterials, has greatly enriched fundamental science and technology. Achieving high selectivity of covalent coupling reactions remains challenging due to the complicated reactivity of organic groups and irreversibility of covalent bonds. Only a few on-surface covalent coupling reactions are frequently used, and this Perspective focuses on the development and synthetic applications of on-surface cross-coupling reactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Yaowen Liu, Pengfei Li, Yanwei Wang, Youai Qiu
Summary: Electrochemistry employs electrons as an efficient and sustainable alternative to chemical oxidants or reductants, and has gained popularity for selective organic synthesis. The combination of electrochemistry with readily available electrophiles has emerged as a viable method for constructing challenging C-C and C-heteroatom bonds. This mini-review provides a systematic summary of the recent advances in electroreductive cross-electrophile coupling (eXEC) reactions, focusing on aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Lukas Hoff, Simon D. Schnell, Andrea Tomio, Anthony Linden, Karl Gademann
Summary: A silver-mediated Pd-catalyzed cross-coupling method for 3-bromo-1,2,4,5-tetrazine with boronic acids was presented in this study. It was found that electronic modification of the dppf ligand played a crucial role in achieving good turnover. Using this fast method, a variety of alkyl-, heteroatom-, and halide-substituted aryl- and heteroaryl-tetrazines were successfully prepared, with yields up to 87%.
Review
Chemistry, Organic
Vipin K. Maikhuri, Vineet Verma, Ankita Chaudhary, Divya Mathur, Rajesh Kumar, Ashok K. Prasad
Summary: Multicomponent reactions (MCRs) are a strategic chemical transformation involving three or more reactants in one pot to produce a functionalized final product. This method is ideal for achieving high complexity, diversity, yields, atom efficiency, and faster reaction times. Sugars, as naturally occurring compounds, have various hydroxy groups and defined stereochemistry, making them attractive for drug discovery. However, their potential in MCRs has only recently been realized. This article presents recent advances in the synthesis of sugar-derived heterocycles using MCRs, aiming to encourage the application of this powerful chemistry in generating novel glycoconjugate challenges.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Zhenghong Zhou, Jimin Yang, Bo Yang, Yang Han, Lijuan Zhu, Xiao-Song Xue, Feng Zhu
Summary: This study presents a pioneering example of nickel-catalysed enantioconvergent Stille cross-coupling reactions. The reactions result in the formation of C-C bonds in good to high yields with excellent stereoselectivity, providing a practical and cost-effective method for synthesis. The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process, opening up new research possibilities in the field of Stille reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Bryan C. Figula, D. Lucas Kane, Kaluvu Balaraman, Christian Wolf
Summary: Cross-coupling of alkyl fluorides and organocuprates is achieved via aluminum halide mediated C-F bond activation, leading to the formation of Csp2-Csp3 and Csp3-Csp3 bonds. The reaction exhibits mild conditions and effectively controls competing side reactions, resulting in high yields and good functional group tolerance.
Article
Chemistry, Multidisciplinary
Diego Madronero, Cesar A. Mujica-Martinez, Alfredo Vazquez
Summary: Lithium anions derived from O-carbonate-protected cyanohydrins undergo conjugate addition to cycloalkenones with the concomitant transfer of the alkoxycarbonyl group to produce tricarbonyl compounds. These products offer various possibilities for further development, as demonstrated by the formation of bicyclic and tricyclic systems through intramolecular condensation reactions.
Article
Chemistry, Multidisciplinary
Hikaru Yanai, Teru Kawazoe, Nobuyuki Ishii, Bernhard Witulski, Takashi Matsumoto
Summary: In this study, 4-aryl-1,3-dihydroxy-2-naphthoates with the less accessible 1,2,3,4-tetrasubstituted naphthalene scaffold were selectively synthesized from brominated lactol silyl ethers through the 1,2-aryl-migrative ring rearrangement reaction, showing photoluminescence emission in both solid state and solutions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Kirsten A. Hewitt, Pei-Pei Xie, Taylor A. Thane, Nadia Hirbawi, Shuo-Qing Zhang, Alissa C. Matus, Erika L. Lucas, Xin Hong, Elizabeth R. Jarvo
Summary: A nickel-catalyzed domino reaction has been developed that utilizes sulfonamide, alkyl chloride, and alkyne functional groups to synthesize novel compounds with valuable applications in medicinal chemistry. The method involves a multistep sequence starting from ynals through iron-promoted aza-Prins reactions, leading to the formation of vinylcyclopropanes bearing tetrasubstituted olefins. Experimental and computational results support the proposed mechanism of the catalytic cycle, with a key ambiphilic allenylnickel intermediate leading to a bifurcated reaction pathway that generates olefin isomers.
Article
Chemistry, Multidisciplinary
Hitomi Tsuno, Jingfeng Shen, Hiroki Komatsu, Norihito Arichi, Shinsuke Inuki, Hiroaki Ohno
Summary: A gold-catalyzed cascade cyclization of naphthalene-tethered allenynes leads to strained fused phenanthrene derivatives. The reaction involves the nucleophilic reaction of an alkyne with an activated allene to generate a vinyl cation intermediate, followed by arylation with a tethered naphthalene ring to form the 4H-cyclopenta[def]phenanthrene (CPP) scaffold. The gold-catalyzed reaction of aryl-substituted substrates on the alkyne terminus also produces dibenzofluorene derivatives alongside the CPP derivatives, depending on the reaction conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Multidisciplinary Sciences
Indrajit Ghosh, Nikita Shlapakov, Tobias A. Karl, Jonas Dueker, Maksim Nikitin, Julia V. Burykina, Valentine P. Ananikov, Burkhard Koenig
Summary: Adaptive dynamic homogeneous catalysis (AD-HoC) with nickel under visible-light-driven redox reaction conditions allows for general C(sp(2))-(hetero)atom coupling reactions with various nucleophiles. The self-adjustive nature of the catalytic system simplifies the classification and optimization process, resulting in predictable reaction conditions and hundreds of synthetic examples.
Article
Chemistry, Organic
Kumud Sharma, Kashmiri Neog, Pranjal Gogoi
Article
Chemistry, Organic
Abhilash Sharma, Hemanta Hazarika, Pranjal Gogoi
Summary: In recent years, o-quinone methides and o-quinone sulfides have been widely recognized as reactive intermediates in the synthesis of diversely functionalized ortho-disubstituted arenes and heterocycles. This synopsis provides a comprehensive overview on the potential applications of these compounds in the one-pot synthesis of ortho-disubstituted arenes and heterocycles via arynes, highlighting their importance in organic synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hemanta Hazarika, Kangkana Chutia, Babulal Das, Pranjal Gogoi
Summary: An aryne-based synthetic protocol has been developed for the synthesis of 3-substituted-3-hydroxy-indolin-2-ones, yielding a wide variety of products in good yields. One of the synthesized compounds has been confirmed by single crystal XRD analysis. Treating the synthesized derivatives with an inorganic base at high temperature leads to an interesting o-arylated product of 1,3-cyclohexandione.
NEW JOURNAL OF CHEMISTRY
(2021)
Review
Chemistry, Organic
Manashi Sarmah, Kangkana Chutia, Dhiraj Dutta, Pranjal Gogoi
Summary: Coumarin-fused-coumarins have gained significant attention in the scientific community for their versatile applications in interdisciplinary fields. Various synthetic pathways have been developed to create novel analogues with interesting photophysical properties. This review focuses on the synthetic strategies and photophysical properties of diverse coumarin-fused-coumarins.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Amar Jyoti Bhuyan, Sourav Jyoti Bharali, Abhilash Sharma, Dhiraj Dutta, Pranjal Gogoi, Lakhinath Saikia
Summary: This research presents a novel synthetic methodology for phenoxypyrimidines without the direct use of phenols or their salts. Unlike the conventional approach, the reaction between chloropyrimidines and arylboronic acids led to the formation of C-O bonds under specific conditions. A total of 25 phenoxypyrimidines were successfully synthesized, among which 6 shared structural resemblance to etravirine.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Kangkana Chutia, Manashi Sarmah, Pranjal Gogoi
Summary: The isocoumarin framework's versatility allows access to a wide range of pharmacological targets. This unique heterocycle core, found in natural products and organic molecules, contributes to medicinal chemistry as anti-cancer, anti-inflammatory, and immunomodulatory agents. The appealing properties of its analogues have prompted scientists to explore their synthetic counterparts. In this review, we provide an update on the synthesis of 3-substituted and 3,4-disubstituted isocoumarins, covering a comprehensive survey of catalytic methods, functionalizations, and possible mechanistic aspects.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Manashi Sarmah, Deep Jyoti Das, Dhiraj Dutta, Rinku Baishya, Pranjal Gogoi
Summary: A Pd-catalyzed method for the direct synthesis of benzo[a]carbazoles from internal alkynes and N-tosyl-iodoindoles has been demonstrated. This method allows the synthesis of electronically different benzo[a]carbazoles with good yields. The synthesized compounds showed potent anticancer activity against human lung and breast cancer cells.
Article
Chemistry, Multidisciplinary
Dhiraj Dutta, Rajshree R. Nair, Sreejith Mangalath, S. Asha Nair, Joshy Joseph, Pranjal Gogoi, Danaboyina Ramaiah
Summary: In this study, two novel biocompatible sensitizers based on aza-BODIPYs incorporated with heavy atoms and biotin moieties were synthesized for the development of efficient photosensitizers for cancerous tissues. The resulting bioconjugates DPR2a and DPR2b showed favorable absorption range, high triplet-state quantum yields, and singlet oxygen generation yields. In vitro and in vivo studies confirmed their rapid cellular uptake, negligible dark toxicity, and high photocytotoxicity, making them promising for cancer imaging and photodynamic therapy.
Article
Chemistry, Multidisciplinary
Dhiraj Dutta, Rajshree R. Nair, Nasib Kayastha, S. Asha Nair, Pranjal Gogoi
Summary: Aza-BODIPY biotin-based nano-self-assembly with a biotin receptor was designed for selective NIR turn-on fluorescence activity against cancer cells. The nanostructured aza-BODIPY assemblies exhibited unique fluorescence characteristics through an avidin-induced partial disintegration process. In vitro studies showed that nanoprobes NSA-DPR1a and NSA-DPR1b effectively recognized and could discriminate biotin receptor-positive cancer cells (MDA-MB-231 and MCF7) compared to non-cancerous cells (MCF10A).
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Dhiraj Dutta, Rajshree R. Nair, Kashmiri Neog, S. Asha Nair, Pranjal Gogoi
Summary: In this study, two BODIPY-biotin conjugates were designed and synthesized for targeted photodynamic therapy applications. Both conjugates showed good absorption with high molar absorption coefficients and decent singlet oxygen generation quantum yields. They were localized in the mitochondria and exhibited excellent photocytotoxicity in MDA-MB-231 breast cancer cells.
RSC MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Amar Jyoti Bhuyan, Sourav Jyoti Bharali, Abhilash Sharma, Dhiraj Dutta, Pranjal Gogoi, Lakhinath Saikia
Summary: This study presents a synthetic method for phenoxypyridine that does not require the direct use of phenols or their salts. The reactions between chloropyrimidines and arylboronic acids instead of aryl or alkyl halides led to the formation of C-O bonds. A total of 25 phenoxypyrimidines were successfully synthesized using this protocol, with 6 of them sharing structural similarities with etravirine.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Hemanta Hazarika, Pranjal Gogoi
Summary: Arynes are highly reactive transient intermediates with enormous applications in organic synthesis. Aryne chemistry has shown incredible developments in carbon-carbon and carbon-heteroatom bond formation reactions over the last three decades. One aspect of development in this field involves C-S bond formation under mild conditions, which has a tremendous scope for the synthesis of various important organosulfur building blocks.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Kumud Sharma, Kashmiri Neog, Abhilash Sharma, Pranjal Gogoi
Summary: A Pd(ii)-catalyzed oxidative alkenylation of 4-hydroxycoumarins with maleimides for the synthesis of 4-hydroxy-3-maleimidecoumarins has been developed. This methodology involves C-H activation and C(sp(2))-C(sp(2)) bond formation to provide a range of alkenylated Heck-type products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Abhilash Sharma, Dhiraj Dutta, Pranjal Gogoi
Summary: A palladium-catalyzed cascade strategy has been developed for the one-pot synthesis of functionalized spiro(indoline-3,2'-quinazolin)-2-one derivatives from readily available starting materials, offering an attractive pathway for the synthesis of a broad range of these compounds in good yields through C-C and two C-N bond formations in a single reaction operation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Organic
Manashi Sarmah, Abhilash Sharma, Pranjal Gogoi
Summary: Due to their transient nature, arynes have remarkable and diverse applications in the synthetic world. Kobayashi's aryne precursor has shown high reactivity and significant advancements in the synthesis of various polycyclic aromatic hydrocarbons with practical utility. This review highlights the extensive use of Kobayashi's aryne intermediates for synthesizing different classes of PAHs.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
