Article
Chemistry, Physical
Patricia C. Lin, Chetan Joshi, Tristan M. McGinnis, Sharath Chandra Mallojjala, Amberly B. Sanford, Jennifer S. Hirschi, Elizabeth R. Jarvo
Summary: A nickel-catalyzed cross-electrophile coupling reaction was developed for the synthesis of enantioenriched cyclopropane products containing vinyl fluoride substituents. The reaction involves the C-F bond activation of allylic gem-difluorides or the C-O bond activation of unactivated alkyl sulfonates. The findings of this study have significant implications in medicinal chemistry.
Article
Chemistry, Organic
Biplab Mondal, Subhadeep Hazra, Ayan Chatterjee, Manveer Patel, Jaideep Saha
Summary: This study developed a catalytic, reductive C-C bond formation method between alkenes and vinyl cyclopropane (VCP) through hydrogen atom transfer (MHAT). Despite the use of VCP as probes in radical-clock experiments, the translation of this method into synthetic methods for accessing elusive C-C bonds remains largely unexplored. This work represents the first exploration in this field, where the high chemoselectivity of MHAT for alkene over VCP was crucial for realizing the strategy. This method has a broad scope, high functional group tolerance, and useful applications.
Article
Multidisciplinary Sciences
Kaluvu Balaraman, Christian Wolf
Summary: This study demonstrates the chemodivergent activation of monofluoroalkyl compounds towards either nucleophilic or electrophilic intermediates, expanding the scope of organofluorine chemistry and creating new synthetic opportunities for carbon-carbon and carbon-heteroatom bond formations.
Article
Chemistry, Physical
Julianna M. Mouat, Jonas K. Widness, Daniel G. Enny, Mahilet T. Meidenbauer, Farwa Awan, Todd D. Krauss, Daniel J. Weix
Summary: This study demonstrates that 5.7 nm CdS quantum dots (QDs) are efficient photocatalysts for photoredox-promoted cross-electrophile coupling with a high turnover number (up to 40,000). NMR studies reveal that triethanolamine-capped QDs serve as the active catalyst and can displace native ligands on the QD surface, highlighting the significance of surface chemistry in catalytic performance.
Article
Chemistry, Organic
Ying Lin, Liang Zou, Renren Bai, Xiang-Yang Ye, Tian Xie, Yang Ye
Summary: We present an easy and efficient method for vinylation using Fe-catalyzed cross-electrophile coupling of readily available vinyl- and hydro-chlorosilanes with a range of substituted alkenyl bromides using manganese as the terminal reductant. This modular approach allows the formation of various vinyl orgaonosilanes, including electron-rich, electron-poor, and ortho-/meta-/para-substituted vinyl electrophiles, with excellent functional group tolerance and broad substrate scope. Furthermore, this method successfully modified substrates with structurally complex natural products and pharmaceutical motifs, demonstrating its potential in gram-scale reactions and derivatization.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Samuel Hruby, Jan Ulc, Ivana Cisarova, Martin Kotora
Summary: The scope of Rh-catalyzed C-C bond cleavage/annulation of biphenylene with various aromatic nitriles was investigated. Further Rh- and Ir-catalyzed C-H bond activation/annulation sequence of the resulting 9-arylphenanthridines with alkynes led to the formation of cationic [4], [5], [6] helical quinolizinium salts. The helical arrangement of these compounds was confirmed by single-crystal X-ray analysis. Most of the prepared quinolizinium salts exhibited fluorescence emission with a maximum wavelength in the range of 525-623 nm and absolute quantum yields up to 25%.
Article
Chemistry, Multidisciplinary
Lili Fang, Shuaixin Fan, Weiping Wu, Tielei Li, Jin Zhu
Summary: A low-cost, room temperature ruthenium catalytic method was developed for the synthesis of delta-diketones by coupling alpha-keto sulfoxonium ylides with cyclopropanols. The mild protocol showed a broad substrate scope (47 examples) and high product yield (up to 99%), with mechanistic studies supporting a cyclopropanol ring opening, sulfoxonium ylide-derived carbenoid formation, migratory insertion C-C bond formation pathway.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Shang-You Sun, Selvam Raju, Guganchandar Vedarethinam, Pei-Lin Chen, Shih-Ching Chuang
Summary: The reaction of o-benzofulvene with TfOH leads to intramolecular cyclization through novel C-C and C-N bond formation, resulting in the formation of a new molecular framework with reasonable to excellent yields. The method tolerates various electron-withdrawing/donating substituents and exhibits high diastereoselectivity. Additionally, it is free of bases, oxidants, and metals, and proceeds under mild reaction conditions favorable for synthetic organic chemistry.
Article
Chemistry, Organic
Austin D. Marchese, Andrew G. Durant, Mark Lautens
Summary: A simple and modular approach using palladium catalysis to synthesize bis-heterocyclic spirocycles is reported. The method leverages a Mizoroki-Heck-type reaction to generate neopentylpalladium species, allowing for intramolecular C-H activation on a wide array of C-H bonds to produce a variety of spirocycles. The reaction is scalable, allowing for easy incorporation of biologically relevant heterocycles without the need for flash column chromatography.
Article
Chemistry, Organic
Ya-Fei Hu, Man-Hang Feng, Peng-Yuan Zhang, Hao Xu, Mengtao Ma, Zhi-Liang Shen, Xue-Qiang Chu
Summary: A chemo-, regio-, and stereoselective reaction has been developed for the synthesis of distinctive gem-fluorophosphine alkenes using trifluoromethylenones, phenylsilane, and phosphine oxides in a sequential hydrodefluorination and defluorophosphorylation relay. This reaction occurs under transition-metal-free conditions and shows good functional group tolerance. The presence of a preinstalled carbonyl auxiliary is crucial for controlling the reactivity of β-trifluoromethylenones and achieving selective functionalization of two fluorine atoms in trifluoromethylated enones.
Article
Chemistry, Applied
Satenik Mkrtchyan, Michal Jakubczyk, Suneel Lanka, Muhammad Yar, Khurshid Ayub, Mohanad Shkoor, Michael Pittelkow, Viktor O. Iaroshenko
Summary: In this study, two mild, solvent-free mechanochemical coupling transformations of CF3 group with nitro compounds were successfully demonstrated, leading to amides or Schiff bases. Ytterbia was used as a catalyst to facilitate the process, which involves C-F bond activation and the use of Si-based reductants/oxygen scavengers. This work represents the first example of utilizing mechanical energy to promote the transformation of the inert CF3 group into other functionalities.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Sanjeev Kumar, Ajay K. Singh
Summary: The study presents the development of a visible-light-driven modular micro-flow reactor for the synthesis of a fused N-heteroaryl scaffold and late-stage functionalization of pyrazolopyridines. The method offers a simple and efficient approach without the need for expensive oxidants or additional photo-catalysts.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yi Jiang, Kai Yang, Yi Wei, Quanquan Wang, Shi-Jun Li, Yu Lan, Ming Joo Koh
Summary: A three-component Ni-catalyzed reductive regime was developed for the selective union of glycosyl halides, organoiodides, and commercially available isobutyl chloroformate as a CO surrogate. This method exhibited strong functionality tolerance and high diastereoselectivity, enabling the efficient synthesis of challenging C-acyl glycosides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Cong Lu, Rui Chen, Rui Wang, Dong Jing, Ke Zheng
Summary: A new approach for the efficient construction of sulfur-containing oxindoles by photoinduced alkene difunctionalization via sulfur 1,2-relocation is developed. The method showed high functional group tolerance and broad substrate compatibility, allowing the synthesis of a library of sulfur-containing oxindole derivatives under mild conditions. Mechanistic investigations revealed the key steps involved the formation of an EDA complex and the generation of alkenes through C-S bond cleavage.
Article
Chemistry, Organic
Cong Lu, Rui Chen, Rui Wang, Dong Jing, Ke Zheng
Summary: A new method for the efficient construction of sulfur-containing oxindoles via photoinduced alkene difunctionalization is developed. The method showed high functional group tolerance and broad substrate compatibility.
Review
Chemistry, Multidisciplinary
Venkataraman Ganesh, Perali Ramu Sridhar, Srinivasan Chandrasekaran
ISRAEL JOURNAL OF CHEMISTRY
(2016)
Review
Chemistry, Organic
Venkataraman Ganesh, Srinivasan Chandrasekaran
SYNTHESIS-STUTTGART
(2016)
Article
Chemistry, Multidisciplinary
Devarajulu Sureshkumar, Venkataraman Ganesh, Naoya Kumagai, Masakatsu Shibasaki
CHEMISTRY-A EUROPEAN JOURNAL
(2014)
Article
Chemistry, Organic
Venkataraman Ganesh, Adam Noble, Varinder K. Aggarwal
Article
Chemistry, Organic
Venkataraman Ganesh, Taraknath Kundu, Srinivasan Chandrasekaran
Article
Chemistry, Organic
Charlotte H. U. Gregson, Venkataraman Ganesh, Varinder K. Aggarwal
Review
Chemistry, Organic
Sourav Mondal, Tamal Ballav, Krishna Biswas, Suman Ghosh, Venkataraman Ganesh
Summary: Palladium-catalyzed cascade reactions have gained much attention in organic synthesis for their efficiency and rapid transformation, serving as a powerful tool for multiple bond formations and reducing cost and time. With a wide range of functional group tolerance, these reactions have been successful in synthesizing complex molecules with biological relevance.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Krishna Biswas, Aniruddha Das, Venkataraman Ganesh
Summary: Organophosphorus catalysis has become a robust platform for introducing boron and silicon functionalities into organic substrates, providing efficient synthetic methodologies. Phosphorus compounds efficiently catalyze various reactions such as hydroboration and silylation in different organic substrates, with the classification of nucleophilic, electrophilic, and biphilic phosphorus catalysts.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Organic
Tamal Ballav, Rajesh Chakrabortty, Aniruddha Das, Suman Ghosh, Venkataraman Ganesh
Summary: This review summarizes the research achievements in the field of synergistic dual catalysis in recent years, highlighting the unique strategies of carbon-carbon and carbon-heteroatom bond formation achieved by combining Pd catalyst with transition metals, Lewis acids, or organocatalysts. The wide applications of these strategies in pharmaceutical and agrochemical industries are also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Suman Ghosh, Rajesh Chakrabortty, Shailendra Kumar, Aniruddha Das, Venkataraman Ganesh
Summary: This paper presents the protoboration of 1,3-diynes as a platform for the iterative functionalization of various groups on enynes and dienes. Synthetic approaches to targets with high complexity are directed toward using small, modular building blocks similar to a Lego construction using iterative chemistry and automated synthesis. Organoboron compounds are currently in the spotlight for achieving these goals. Here, we report an operationally simple, regioselective protoboration of 1,3-diynes using a mixed diboron reagent and Cu(I)/phosphine catalyst to provide enynylboronates in good yields. Under similar conditions, diprotoboration of 1,3-diynes was also achieved to access bench-stable 1,4-diboryl-1,3-dienes in good yields and regioselectivities. The iterative coupling capabilities of the products have been demonstrated along with other downstream transformations offering a range of value-added skeletons.
Article
Chemistry, Organic
Sourav Mondal, Tamal Ballav, Tofayel Sheikh Mohammad, Venkataraman Ganesh
Summary: We present the synthesis and characterization of bis-benzofulvenes, as well as their optical and redox properties. The bis-benzofulvenes were synthesized through Pd-catalyzed intramolecular Heck coupling and Ni(0)-mediated C-(sp(2))-Br dimerization. By tuning the substituents on the exomethylene unit and the aromatic ring, we achieved low optical and electrochemical energy gaps of 2.05 and 1.68 eV. The trends in the energy gaps were compared, and the frontier molecular orbitals were visualized using density functional theory.
Article
Chemistry, Physical
Suman Ghosh, Rajesh Chakrabortty, Shailendra Kumar, Aniruddha Das, Venkataraman Ganesh
Summary: This paper presents a method for protoboration, achieving the synthesis of complex target structures, as well as operationally simple and regioselective reaction conditions for the preparation of products with added value.
Review
Chemistry, Multidisciplinary
Aankhi Khamrai, Venkataraman Ganesh
Summary: This review tracks the journey of free radicals from being uncontrollable to emerging as a powerful tool in chemistry. A modern perspective on the generation of radicals is offered, with a focus on unique strategies in catalyzing radical reactions.
JOURNAL OF CHEMICAL SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Claire M. Wilson, Venkataraman Ganesh, Adam Noble, Varinder K. Aggarwal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2017)
Article
Chemistry, Multidisciplinary
Venkataraman Ganesh, Marcin Odachowski, Varinder K. Aggarwal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2017)