Article
Chemistry, Multidisciplinary
Chaolumen Bai, Bao Chao, Tegshi Muschin, Agula Bao, Menghe Baiyin, Dan Liu, Yong-Sheng Bao
Summary: This study reports the regioselective cross-coupling reactions in the o-methyl benzaldehyde frameworks using palladium catalysis, K2S2O8 or [F+] reagents as oxidants, and unactivated arenes as substrates/solvents. The regiospecificity is controlled by [5,6]-fused or [6,5]-fused palladacycle intermediates formed from Pd-chelation with specific transient directing groups and C-H activations.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Organic
Yilin Kong, Kangning Wei, Guobing Yan
Summary: This review focuses on recent radical coupling reactions via photochemical and electrochemical strategies, as well as the discussion of their mechanisms.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Dong-Yang Han, Xiao-Peng Liu, Ruo-Pu Li, Da-Zhen Xu
Summary: A highly efficient strategy has been developed for the direct thiolation of phenols under transition metal-free and solvent-free conditions. The reactions are operationally simple and employ air as an ideal oxidant, providing mono- and dithiolation products in good to excellent yields under basic conditions. This method tolerates a broad range of aryl thiols and arenes, making it especially applicable for large-scale synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ya-Ting Wen, Xiang-Tao Kong, Hong-Chao Liu, Cui-Tian Wang, Wan-Xu Wei, Bin Wang, Xue-Yuan Liu, Yong-Min Liang
Summary: An innovative 1,5-HAT cascade strategy has been proposed for nickel-catalyzed distal arylation via cross-electrophile coupling. It selectively activates the remote C(sp(3))-H bond through specific migration and uses Ar-I as the available electrophile for constructing the C(sp(3))-C(sp(2)) bond. The method shows broad applicability for benzylic and aliphatic N-fluorocarboxamides with yields up to 80%. Control experiments suggest that this reaction may be initiated by a radical process.
Review
Chemistry, Organic
Aanchal Batra, Pushpinder Singh, Kamal Nain Singh
Summary: Developing greener and atom economical methods for carbon-heteroatom bond formation is crucial in synthetic organic chemistry. Metal-free cross-dehydrogenative coupling (CDC) is an attractive approach due to its ease and environmental friendliness, and this review focuses on recent developments in this area.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Zakhar M. Rubanov, Vitalij V. Levin, Alexander D. Dilman
Summary: This paper describes a method for converting aldehydes to ketones by first forming aldimines, and then utilizing acid-promoted Minisci-type reaction with alkyl radicals generated from esters of N-hydroxylphthalimide under photoredox conditions. Aminyl radical cations formed after the addition of the iminium ions are believed to be key intermediates.
Article
Chemistry, Multidisciplinary
Michael W. Milbauer, Jeff W. Kampf, Melanie S. Sanford
Summary: In this study, we successfully isolated a cyclometalated nickel(IV) complex that is similar to a key intermediate proposed in aminoquinoline-directed C-H functionalization catalysis. The complex undergoes bond-forming reaction under mild conditions and demonstrates the importance of LX-type ligands in stabilizing these nickel(IV) species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhonghua Sun, Jie Yao, Shuliang Ji, Weiyou Zhou, Anwei Wang, Mingyang He, Xianjun Hua, Yupeng Liu
Summary: FeCl2/TBAC was found to exhibit high catalytic activity for the synthesis of indoline-fused tetrahydroisoquinolines using aryltetrahydroisoquinolines and active methylene as reactants. The reaction proceeded through domino coupling reactions between C-sp3-H and C-sp3-H, and subsequently C-sp3-H and C-sp2-H. EPR spectroscopy revealed the presence of catalytically active species (Fe3+OO center dot) and Fe3+, which enhanced the reaction through HAT and SET processes, respectively.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Fangzhi Hu, Zhipeng Sun, Mengzhe Pan, Liang Wang, Lubin Xu, Xiong-Li Liu, Shuai-Shuai Li
Summary: A H2O-promoted controllable synthesis of diverse nitrogen heterocycles was developed using a hydride transfer strategy. Various 3-carboxyl and 3-acyl substituted tetrahydroquinolines and 3,4-dihydroquinolin-2(1H)-ones were obtained via cascade reactions. The methodology's synthetic utility and mechanistic studies were also presented.
Article
Chemistry, Inorganic & Nuclear
Alfredo Pereira, Camilo Albornoz, Oleksandra S. Trofymchuk
Summary: This study presents a data-driven approach to analyze reactions catalyzed using [Cp*Co(CO)I-2]. By analyzing different parameters, the screening process in the laboratory is accelerated to yield favorable combinations. The research also demonstrates the effects of reaction conditions and directing groups on the reaction performance.
Article
Chemistry, Multidisciplinary
Subrata Das, Andreas W. Ehlers, Sima Patra, Bas de Bruin, Buddhadeb Chattopadhyay
Summary: A concept for intermolecular C-N cross-coupling amination has been discovered using tetrazoles and aromatic and aliphatic azides with boronic acids under iron-catalyzed conditions. The reaction follows an unprecedented metalloradical activation mechanism, different from traditional metal-catalyzed C-N cross-coupling reactions. The wide scope of this reaction has been demonstrated by employing various tetrazoles, azides, and boronic acids. Moreover, the reaction has shown potential for applications in medicinal chemistry, drug discovery, and pharmaceutical industries, as demonstrated by late-stage aminations and synthesis of a drug candidate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Muhammad Asif Iqbal, Le Lu, Hina Mehmood, Ruimao Hua
Summary: This study reports a Cs2CO3-promoted cross-coupling reaction of arenes with cyano-/nitro-substituted aryl halides in DMSO to afford biaryls in the absence of ligands. The cyano/nitro groups in biaryls are shown to be useful for further transformations. Additionally, the formation of dibenzofurans from reactions between arenes and 1-bromo-2-iodobenzene is reported. A radical mechanism for the formation of biaryls is proposed based on control experiments and theoretical studies.
Article
Chemistry, Organic
Cong Zhang, Yuhang He, Guanghui An
Summary: Iron-mediated divergent reductive coupling reactions of heteroarenes with alkenes have been developed. By switching the substituent site at the C2 and C4 positions of quinolines, either C2 Minisci alkylation or C4 reductive alkylation could be achieved. These approaches feature mild conditions and sensitive functional group tolerance, which enables the functionalization of natural products and medicines. Mechanism investigation revealed that Fe(dibm)(3) would be a dual promoter for both alkyl radical transfer and generation of the more reactive hydrogen donor Ph(RO)SiH2.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Biochemistry & Molecular Biology
Luis G. Ardon-Munoz, Jeanne L. Bolliger
Summary: Many nitrogen- and sulfur-containing heterocyclic compounds with biological activity have been discovered. This study focuses on the synthesis of benzo[4,5]thiazolo[2,3-c][1,2,4]triazoles, an important class of heterocycles. A new synthetic protocol involving oxidation and subsequent C-H bond functionalization is reported, which provides a short reaction time and high yields.
Review
Chemistry, Organic
Yanping Feng, Xiajuan Ye, Dayun Huang, Sheng-Rong Guo
Summary: The direct alpha-Csp(3)-H functionalization of simple ethers is an important strategy in radical reactions. This review discusses its applications based on different starting materials and analyzes mechanisms such as radical addition, C-H activation, elimination, metal-catalyzed coupling, cyclization, oxidation, and rearrangement.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Yogesh Siddaraju, Kandikere Ramaiah Prabhu
JOURNAL OF ORGANIC CHEMISTRY
(2017)
Article
Chemistry, Organic
Yogesh Siddaraju, Kandikere Ramaiah Prabhu
ORGANIC & BIOMOLECULAR CHEMISTRY
(2017)
Article
Chemistry, Organic
Yogesh Siddaraju, Kandikere Ramaiah Prabhu
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Yogesh Siddaraju, Kandikere Ramaiah Prabhu
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
K. R. Jayakrishnan, M. Tamilarasu, K. Jincy, Alagiri Kaliyamoorthy
TETRAHEDRON LETTERS
(2019)
Article
Chemistry, Organic
Fathima Pilathottathil, Doppalapudi Vineet Kumar, Alagiri Kaliyamoorthy
SYNTHETIC COMMUNICATIONS
(2020)
Article
Chemistry, Organic
Tamilarasu Murugesan, Chinraj Sivarajan, Chithra Mohan Jayakumari, Rajat Kumar Singh, Sivaranjana Reddy Vennapusa, Alagiri Kaliyamoorthy
Summary: In this study, a straightforward access to C2-biarylated indole derivatives was achieved through palladium-catalyzed C-H activation strategy, with yields ranging from 24% to 92%. The UV/visible absorption and fluorescence properties of the resulting products were explored, showing that these compounds may exhibit atropisomerism at room temperature based on calculated dihedral angle and rotational barrier values.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
A. Kalyanakrishnan, Arun Joshy, Abhay Kumar Arya, Alagiri Kaliyamoorthy
Summary: The methods for synthesizing alpha-substituted alkenyl sulfoxides are highly valuable for constructing diverse molecules. This study presents a synthetic route for accessing alpha-substituted alkenyl sulfoxides from alkynes and beta-sulfinyl esters, with a wide substrate scope and scalability. Additionally, a direct synthesis of alkenyl sulfoxides from thiols was demonstrated, with the resulting products easily transformed into benzofuran and sulfonyl derivatives. Mechanistic investigations were conducted to understand the reaction mechanism.
Article
Chemistry, Organic
Fathima Pilathottathil, Sreelakshmi Unnikrishnan, Alagiri Kaliyamoorthy
Summary: A transition-metal-free method for the direct synthesis of heteroaryl sulfoxides has been described. By using fi-sulfinyl esters as the source of the sulfenate ion and a Bronsted base catalyst, the desired heteroaryl sulfoxides were obtained in yields of 30 to 94%.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tamilarasu Murugesan, Afna Elikkottil, Alagiri Kaliyamoorthy
Summary: Herein, we report a palladium-catalyzed regioselective C3-allylic alkylation of 2-aryl imidazopyridines with MBH carbonates. This strategy allows for the synthesis of diverse C3-allylated imidazopyridines, and their structures have been confirmed by X-ray analysis. Furthermore, the reaction can be easily scaled up and the resulting product can be manipulated into synthetically useful entities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Amritha Rayaroth, Afna Elikkottil, Chithra Mohan Jayakumari, Kalyanakrishnan Arayil Vennoli, Sivaranjana Reddy Vennapusa, Alagiri Kaliyamoorthy
Summary: We have developed a method for regioselective allenylation and propargylation using unfunctionalized 2-alkynyl azaarenes as pronucleophiles with the appropriate choice of base. The reaction can be directed towards either the formation of allenylated or propargylated products using different bases. Additionally, this strategy is scalable and can be performed on a gram scale.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Amritha Rayaroth, Rajat Kumar Singh, A. Kalyanakrishnan, Krishna Hari, Alagiri Katiyamoorthy
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Yogesh Siddaraju, Kandikere Ramaiah Prabhu
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
