Article
Chemistry, Organic
Yan-Ying Cui, Jin-He Na, Meng-Meng Guo, Jie-Ying Huang, Xue-Qiang Chu, Weidong Rao, Zhi-Liang Shen
Summary: Efficient cobalt-catalyzed cross-couplings of nitrogen-containing heterocyclic phosphonium salts with arylmagnesium halides were achieved in tetrahydrofuran at ambient temperature, using cobalt(II) catalyst and copper(I) salt as catalysts and producing the desired arylated compounds in modest to good yields.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Kui Wang, Xiaoyu Liu, Siyu Yang, Yan Tian, Mingyang Zhou, Jianhua Zhou, Xiaofei Jia, Baoying Li, Siyuan Liu, Jianbin Chen
Summary: Molecular electrophotocatalysis is a powerful strategy for sustainable synthesis, and has been applied in a versatile electrophotocatalytic deaminative alkylation approach. The key point lies in the in situ recycling of alkyl radicals, and the method has also been successfully applied in ligand modification and late-stage functionalization of pharmaceuticals.
Article
Chemistry, Organic
Anna C. Vetter, Declan G. Gilheany, Kirill Nikitin
Summary: Contrary to common belief, the use of strong bases in Wittig chemistry is unnecessary, as novel ion-pair phosphonium carboxylate reagents have been developed for efficient and clean olefination of aldehydes and hemiacetals. These reagents are easily prepared and can be stored as ylides.
Article
Chemistry, Organic
Dmitry Bugaenko, Marina A. Yurovskaya, Alexander Karchava
Summary: By utilizing a umpolung strategy, the reaction of pyridine-N-oxides with Ph3P under developed conditions provides a route to (pyridine-2-yl)phosphonium salts, allowing the selective functionalization of the pyridine ring at the C2 position without the use of unstable organometallic reagents. The protocol, operating at ambient temperature, is tolerant of sensitive functional groups and enables the synthesis of challenging compounds.
Article
Chemistry, Organic
Meiqi Zhu, Wen Yu, Qin Zhong, Benqiang Cui, Changsheng Cao, Yanhui Shi
Summary: The Suzuki cross-coupling reaction of triphenyl quaternary phosphonium triflates with boronic acids was successfully achieved using Ni(COD)2 as the catalyst without an additional ligand. Cs2CO3 was used as the base in toluene, and diverse biphenyls were synthesized with medium to excellent yields. This scalable method displayed wide adaptability towards boronic acids and tolerated various functional groups. Regioselective arylation was observed on the electron-deficient phenyl group of differentially substituted phenyl phosphonium triflates. (c) 2023 Elsevier Ltd. All rights reserved.
Article
Chemistry, Multidisciplinary
Xiang-Lei Han, Bin Hu, Chao Fei, Zhe Li, Yang Yu, Cheng Cheng, Bruce Foxman, Jisheng Luo, Li Deng
Summary: This study reports an unprecedented catalytic asymmetric cross-coupling reaction that allows a variety of ketimines and aldimines to react, resulting in the direct synthesis of chiral vicinal diamines. This reaction is enabled by the development of a new chiral ammonium catalyst, which leads to highly diastereo- and enantioselective formation of diverse chiral vicinal diamines. It establishes a new approach for the asymmetric synthesis of chiral vicinal diamines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jia-Jia Liao, Ren-Gui Tian, Shi-Kai Tian
Summary: An unprecedented reductive cross-coupling reaction has been developed through C-N bond cleavage, enabling the efficient synthesis of diverse alkene products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Mengwan Yang, Jiaxi Fang, Huan Liu, Xinyao Lu, Jiawen Zhou, Zehuai Mou, Huifei Wang
Summary: In this study, a manganese-mediated reductive alkylation reaction was developed for the formation of C2-alkylated benzothiazoles by reacting benzyl bromides with heterocyclic thiazolyl-phosphonium salts. The reaction displayed a wide substrate scope, high-functional-group tolerance, and could be applied for late-stage modification of complex natural products and bioactive molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Yan-Ying Cui, Wen-Xin Li, Na-Na Ma, Chuanji Shen, Xiaocong Zhou, Xue-Qiang Chu, Weidong Rao, Zhi-Liang Shen
Summary: The direct cross-coupling of heterocyclic phosphonium salts with aryl bromides was successfully achieved at ambient temperature in THF using a nickel(ii) catalyst and other auxiliary reagents, providing an easy access to 4-arylated pyridine, quinoline, quinoxaline, and pyrazine.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Sai Rohini Narayanan Kolusu, Manuel Nappi
Summary: In this study, a metal-free method for the deoxygenative coupling of alcohol-derived benzoates and pyridines promoted by visible light is reported. The protocol shows wide substrate scope and broad applicability, even in the context of late-stage functionalization and DNA-drug coupling reactions.
Article
Chemistry, Multidisciplinary
Xiaoyu Tong, Ze-Peng Yang, Carlos E. Del Angel E. Aguilar, Gregory C. Fu
Summary: This study reports an iron catalyst for cross-coupling reactions of alkyl electrophiles using olefins and hydrosilanes instead of alkylmetal reagents. Carbon-carbon bond formation occurs at room temperature, and the method utilizes commercially available components. Mechanistic studies suggest the generation of an alkyl radical from the alkyl electrophile and reversible elementary steps.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Simone Grosso, Marcelina Mlynczak, Gwilherm Evano, Olivier Riant
Summary: An efficient and unprecedented cross-coupling reaction between acylzirconocenes and diaryliodonium tetrafluoroborates is reported. This method utilizes acylzirconocenes, readily prepared starting materials, and a low pressure of in situ generated carbon monoxide to synthesize a variety of alkyl-aryl-ketones under simple copper cyanide catalysis, without the need for additional ligands.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kazuho Ban, Keisuke Imai, Shuki Oyama, Jin Tokunaga, Yui Ikeda, Hiromasa Uchiyama, Kazunori Kadota, Yuichi Tozuka, Shuji Akai, Yoshinari Sawama
Summary: In this study, a novel concept for preparing deuterated reagents was established and the deuterium kinetic isotope effects were demonstrated for the first time. This research has significant implications for drug discovery based on deuterium chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zi-Tong Pan, Xu-Kuan Qi, Qian Xiao, Xi-Wen Liang, Jian-Ji Zhong, Jing-Xin Jian, Qing-Xiao Tong
Summary: In this study, we have demonstrated a regulable cross-coupling reaction using alcohols as alkylating reagents to functionalize benzothiazoles. We obtained two types of cross-coupling products with high isolated yields, opening up a broad research prospect for expanding alcohols as alkylating reagents.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Xing-Yu Wang, Xiao-Bing Wang, Yin Tian, Cheng Peng, Ming-Sheng Xie, Hai-Ming Guo
Summary: A highly enantioselective dearomative [3 + 2] annulation reaction was achieved using quinolines, isoquinolines, and pyridines with donor-acceptor aminocyclopropanes. By utilizing a C-1-symmetric imidazoline-pyrroloimidazolone pyridine as the tridentate ligand and Co(OTf)2 as the Lewis acid, chiral indolizidine and benzo-fused indolizidine derivatives were obtained with good yields (up to 98%), excellent diastereoselectivities (>20:1 dr), and excellent enantioselectivities (up to 98% ee). Mechanistic experiments and DFT calculations revealed that the tridentate nitrogen ligand acted as a bifunctional chiral ligand, coordinating with the Co(II) salt and forming a H-bond to facilitate the nucleophilic attack of N-heteroaromatics and achieve high enantioselectivity.
Article
Chemistry, Multidisciplinary
Ryan D. Dolewski, Patrick J. Fricke, Andrew McNally
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Multidisciplinary
J. Luke Koniarczyk, David Hesk, Alix Overgard, Ian W. Davies, Andrew McNally
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Organic
Chirag Patel, Margaret Mohnike, Michael C. Hilton, Andrew McNally
Article
Chemistry, Multidisciplinary
Ryan G. Anderson, Brianna M. Jett, Andrew McNally
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Multidisciplinary Sciences
Michael C. Hilton, Xuan Zhang, Benjamin T. Boyle, Juan V. Alegre-Requena, Robert S. Paton, Andrew McNally
Article
Chemistry, Multidisciplinary
Benjamin T. Boyle, Michael C. Hilton, Andrew McNally
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
J. Luke Koniarczyk, Jacob W. Greenwood, Juan Alegre-Requena, Robert S. Paton, Andrew McNally
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Jeffrey N. Levy, Juan Alegre-Requena, Renrong Liu, Robert S. Paton, Andrew McNally
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Benjamin T. Boyle, J. Luke Koniarczyk, Andrew McNally
Summary: The N-phosphonium pyridinium intermediates exhibit unusual reactivity in pyridine SNAr reactions. The activation mode described in this study allows for ambient temperature C-P bond formation and is effective across a wide range of substrates.
Article
Multidisciplinary Sciences
Xuan Zhang, Kyle G. Nottingham, Chirag Patel, Juan V. Alegre-Requena, Jeffrey N. Levy, Robert S. Paton, Andrew McNally
Summary: Fluoroalkyl groups have significant effects on the physical properties of pharmaceuticals and impact various metrics related to their pharmacokinetics and pharmacodynamics. The development of new fluoroalkylation reactions has led to the direct conversion of C-H bonds into complex C-CF2X groups in drug-like molecules. A novel approach using bench-stable fluoroalkylphosphines allows for the selective conversion of C-H bonds in pyridine building blocks and pharmaceuticals without the need for preinstalled functional groups or directing groups.
Article
Chemistry, Multidisciplinary
Patrick J. Fricke, Ryan D. Dolewski, Andrew McNally
Summary: The method presents a distinct approach to constructing 4-alkylpyridines using dearomatized pyridylphosphonium ylide intermediates. Pyridine N-activation is crucial, enabling coupling between a wide variety of substituted pyridines and aldehydes. This approach provides an alternative to metal-catalyzed sp(2)-sp(3) cross-coupling reactions and Minisci-type processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Benjamin T. Boyle, Jeffrey N. Levy, Louis de Lescure, Robert S. Paton, Andrew McNally
Summary: This study reports a new method for pyridine halogenation reactions, which involves a reaction sequence of pyridyl ring opening, halogenation, and ring closing to achieve highly regioselective halogenation reactions on pyridine precursors. Experimental and computational mechanistic studies show that the nature of the halogen electrophile can modify the selectivity-determining step.
Review
Chemistry, Multidisciplinary
Celena M. Josephitis, Hillary M. H. Nguyen, Andrew McNally
Summary: Azines, such as pyridines, quinolines, pyrimidines, and pyridazines, are widely used in pharmaceuticals due to their physiochemical properties and tunability. Synthetic methods for installing groups from azine C-H bonds are valuable, especially in late-stage functionalization reactions. This review highlights recent advances in azine late-stage functionalization reactions.
Article
Chemistry, Multidisciplinary
Jacob W. Greenwood, Benjamin T. Boyle, Andrew McNally
Summary: Radical couplings of cyanopyridine radical anions offer a valuable technology for functionalizing pyridines in pharmaceuticals, agrochemicals, and materials. This study demonstrates that pyridylphosphonium salts can be useful alternatives to cyanopyridines in radical-radical coupling reactions, expanding the scope of complex pyridines. Additionally, late-stage functionalization of pharmaceuticals is highlighted as an advantage of pyridylphosphonium salts over cyanopyridines.