Article
Chemistry, Organic
Wenjun Miao, Chuanfa Ni, Pan Xiao, Rulong Jia, Wei Zhang, Jinbo Hu
Summary: This novel nickel-catalyzed reductive cross-coupling reaction allows the formation of C(sp(2))-C(sp(2)) bonds through selective C(sp(2))-S bond cleavage, showcasing the new reactivity of 2-PySO2CF2H reagent. The use of readily available nickel catalyst and sulfones as coupling partners enables facile access to biaryls under mild reaction conditions without pregeneration of arylmetal reagents.
Article
Chemistry, Organic
Qinyu Luo, Xiu Wang, Jinbo Hu
Summary: The introduction of fluorine atoms into a carbon-carbon double bond can significantly alter the physical, chemical, and biological properties of a target molecule. Fluorinated alkenes, which are important compounds widely used in medicinal chemistry and materials science, can be synthesized through the Julia and Julia-Kocienski reactions using a-fluorinated sulfones. This review summarizes the methods for synthesizing fluorinated alkenes through Julia and Julia-Kocienski reactions, categorizing them based on target molecules and sulfone reagents, and highlights the unique effect of fluorine substituents.
Review
Chemistry, Organic
Guna Sakaine, Zigmars Leitis, Rebeka Locmele, Gints Smits
Summary: This review summarizes the scientific literature of the past decade, focusing on the key aspects for successful execution of the olefination step. The main stereoselectivity and yield-determining aspects have been outlined, providing all the necessary information for the synthesis of Julia-Kocienski reagents as well as the most commonly used reaction optimization techniques.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Konstantinos A. A. Ouzounthanasis, Stergios R. R. Rizos, Alexandros E. E. Koumbis
Summary: The Julia-Kocienski olefination, a coupling reaction between a carbonyl component and a sulfone partner, has become an important tool in the synthetic toolbox for preparing various organic compounds. Recent studies have focused on the synthesis of trisubstituted alkenes and understanding their stereoselectivity. This review provides a comprehensive overview of the progress and developments in the application of Julia-Kocienski olefination for the synthesis of trisubstituted alkenes, which are valuable precursors for natural products, analogs, and biologically important compounds. The review also discusses key methodologies, optimal conditions, stereoselectivities, and new modifications and approaches.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wei Du, Qinyu Luo, Zhiqiang Wei, Xiu Wang, Chuanfa Ni, Jinbo Hu
Summary: In this study, a novel nickel-catalyzed reductive coupling method was reported, enabling the difluoromethylation reaction between aryl iodides and 2-PySO2CF2H reagent without pre-generation of arylmetal reagents.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Makoto Inai, Yoshinori Ueno, Hiroto Sagara, Hitoshi Ouchi, Fumihiko Yoshimura, Toshiyuki Kan
Summary: This study presents the first total synthesis of isosilybin B (4) and introduces a synthetic strategy that utilizes the modified Julia-Kocienski olefination reaction and the construction of a quinomethide intermediate.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Pulluparambil Xavier Thresia Rinu, Sankaran Radhika, Gopinathan Anilkumar
Summary: The Julia-Kocienski (J-K) olefination is a modified version of Julia-Lythgoe olefination, widely used in the synthesis of E-alkenes for natural product synthesis. It has shown efficient protocols and recent developments in this area, providing a key step in the synthesis of various natural products.
Article
Chemistry, Organic
Dharma Theja Nannapaneni, Kiran Chinthapally, Ishita Hatial, Brandon L. Ashfeld, Brian S. J. Blagg
Summary: An efficient seven-step procedure for the synthesis of (25R)-cholesta-5,7-diene-36,26-diol from commercially available ergosterol in a yield of 25% is described. The synthesis involves Julia-Kocienski olefination of the aldehyde with benzothiazole sulfone ester in the presence of LiHMDS followed by reduction of the alkene. This research provides important insights and potential applications.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Ekaterina Lerman, Shlomo Levinger, Amnon Albeck
Summary: The study developed a method for synthesizing optically active C-terminal building blocks and expanded it to building blocks with side chains functionalized with oxygen, nitrogen, or halogen. The key step is the enzymatic hydrolysis introducing optical activity, while the ordering of subsequent chemical reactions will determine the absolute stereochemistry of the final building blocks.
Article
Chemistry, Organic
Paul C. Ruer, Youssef Nassar, Peter Polak, Janine Cossy
Summary: Five-membered exo-glycals were synthesized from six-membered 2-iodo-endo-glycals through a metal/halogen exchange/ring-opening sequence followed by a cyclization catalyzed by Ag2CO3.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Vasiliy M. Muzalevskiy, Zoia A. Sizova, Vladimir T. Abaev, Valentine G. Nenajdenko
Summary: The catalytic olefination reaction of 2-nitrobenzaldehydes with CF3CCl3 can stereoselectively afford trifluoromethylated ortho-nitrostyrenes in up to 88% yield, which can then be further transformed into 2-CF3-indoles with broad synthetic scope and high yields.
Article
Chemistry, Organic
Mamta Yadav, Ram Singh Jat, Bibek Sarma, M. Bhanuchandra
Summary: The Pd(II)-catalyzed C-H olefination of aryl 2-pyridyl sulfoxides with unactivated and activated olefins was successfully demonstrated using environmentally benign molecular oxygen as the sole oxidant. The versatile nature of the 2-pyridyl sulfoxide directing group was confirmed by its transformation to the sulfone functionality. Deuterium scrambling experiments and intramolecular kinetic isotopic studies provided insights into the reaction pathway.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Wei Hao, Candice L. Joe, Andrea Daru, Sloan Ayers, Antonio Ramirez, Bhupinder Sandhu, Ryan A. Daley, Jason S. Chen, Michael A. Schmidt, Donna G. Blackmond
Summary: The mechanism of asymmetric hydrogenation of 2-pyridyl alkenes catalyzed by chiral Rh-phosphine complexes has been studied at ambient temperature. The reaction involves reversible substrate binding followed by rate-determining hydrogen addition. Substrate binding occurs only through the pyridine nitrogen and is not influenced by hydrogen pressure. Catalyst deactivation is observed due to the presence of an off-cycle Rh-hydride species. The stereochemical outcome in this system correlates with the relative stability of the E and Z rotamers of the substrate.
Review
Chemistry, Organic
Yuma Wakamiya, Tohru Oishi
Summary: AM3, a secondary metabolite isolated from the dinoflagellate Amphidinium krebsi, has potent antifungal and hemolytic activities. After years of research, its absolute configuration was confirmed and its true structure was obtained through total synthesis.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Qinghe Liu, Chuanfa Ni, Qian Wang, Depei Meng, Jinbo Hu
Summary: This article outlines an efficient method for the stereoselective introduction of the difluoro(aminosulfonyl) methyl group (CF2SO2NH2) into carbonyls, imines, and alkyl halides. The method provides a unique solution for the synthesis of chiral alpha,alpha-difluorinated sulfonamides with a quaternary stereocenter. The effectiveness of this method is demonstrated through the synthesis of fluorinated analogues of bioactive compounds and the late-stage modification of complex molecules.
Article
Chemistry, Multidisciplinary
Depei Meng, Yichong Lyu, Chuanfa Ni, Min Zhou, Yang Li, Jinbo Hu
Summary: (Trifluoromethyl)benzothioate is an inexpensive, stable, and user-friendly trifluoromethylthiolation reagent that can be used in various synthetic reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Guangwu Sun, Herui Liu, Xiu Wang, Wenbo Zhang, Wenjun Miao, Qinyu Luo, Bing Gao, Jinbo Hu
Summary: In this manuscript, a novel palladium-catalyzed coupling reaction between gem-difluoroalkenes and aryl boronic acids is reported, which yields bioactive indane-type ketones with an all-carbon alpha-quaternary center. The mechanism involves a water-induced defluorination and cross-coupling cascade pathway, supported by characterization and stoichiometric reactions of the key intermediates RCF2PdII. The use of vinyl difluoromethylene motif as an in situ carbonyl precursor is unprecedented in transition-metal-catalyzed coupling reactions, and it is expected to spark broad interest in ketone synthesis, fluoroalkene functionalization, and design of new synthetic protocols based on the unique reactivity of difluoroalkyl palladium(II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
An Liu, Chuanfa Ni, Qiqiang Xie, Jinbo Hu
Summary: We have developed a new strategy for controllable CF2 insertions into C-H bonds of aldehydes under transition-metal-free conditions. The success of this strategy relies on the formation of well-defined intermediates using the difluorocarbene reagent TMSCF2Br. These intermediates can react with various electrophiles, leading to the synthesis of diverse ketones containing CF2 and CF2CF2 units.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Zhenchuang Xu, Yanchuan Zhao
Summary: Nuclear magnetic resonance (NMR) is a unique analytical technique that provides atomic-level structural information about molecules. By combining 19F NMR with ingeniously designed molecular probes, the dynamic recognitions of target analytes can be easily interpreted as characteristic 19F NMR signals. This method shows robust performance in the precise analysis of complex mixtures and chiral analytes.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jiayu Jiang, Lixian Wen, Hongshuang Wang, Xiaoguang Chen, Yanchuan Zhao, Xiaohui Wang
Summary: The abuse of amphetamine-type stimulants (ATS) is a global problem. In this study, a recognition-enabled chromatographic (REC) 19F nuclear magnetic resonance (NMR) method was developed for the detection and quantitative analysis of ATS. This method allows for the detection and differentiation of up to 20 ATS and structurally similar analogs in complex mixtures, and has the capability to quantitatively detect ATS at a concentration of 1 μM in artificial urine. The results demonstrate that REC 19F NMR is an efficient and robust strategy for the determination of ATS and related derivatives.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Analytical
Jinhua Liang, Zhenchuang Xu, Jian Wu, Yanchuan Zhao
Summary: A 19F-labeled gallium-based probe was developed for the enantiodifferentiation of various chiral analytes. It showed stronger affinity towards the amino group compared to the hydroxy group, simplifying the 19F NMR signals for analytes with multiple Lewis basic sites. This probe can be used for assessing the enantiomeric excess values of crude products obtained in asymmetric reactions without purification.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhenchuang Xu, Yanchuan Zhao
Summary: NMR technique is powerful but hindered by crowded spectra when analyzing complex real-world samples. This account summarizes the development of novel F-19-labeled probes for separation-free multicomponent analysis. Strategies for chiral discrimination, sensitivity enhancement, and automated analyte identification are discussed.
Article
Chemistry, Inorganic & Nuclear
Yongxi Li, Guangwu Sun, Xihang He, Honggui Lv, Bing Gao
Summary: An intramolecular annulation strategy has been developed for the synthesis of fluoroalkylated indane-type analogs. The difluoromethyl and trifluoromethyl functional motifs can be obtained from gem-difluoroalkenes through this palladium-catalyzed reaction. This method can also be extended to other fluoroalkenes and multi-component reactions.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Organic
Yang -yang Li, Bing Gao
Summary: N-functionalization of free sulfoximines is a significant method for modifying their properties for various applications. This study presents a rhodium-catalyzed N-allylation of free sulfoximines (=NH) with allenes, enabling chemo- and enantioselective ?-hydroamination of allenes and gem-difluoroallenes. The synthesis of sulfoximine products using this method is also demonstrated.
Article
Chemistry, Multidisciplinary
Guangxing Gu, Zhenchuang Xu, Lixian Wen, Jinhua Liang, Chenyang Wang, Xiaolong Wan, Yanchuan Zhao
Summary: We report a chemosensing approach based on F-19 NMR for rapid detection and differentiation of chiral N-heterocyclic compounds. The method utilizes dynamic binding between analytes and a chiral F-19-labeled palladium probe to create characteristic F-19 NMR signals for each enantiomer, allowing effective recognition of bulky analytes.
Article
Chemistry, Analytical
Yushu Jia, Lixian Wen, Wenjing Bao, Zhenchuang Xu, Jian Wu, Yanchuan Zhao
Summary: In this study, chiral NMR probes labeled with a significant number of chemically equivalent F-19 atoms are used to overcome the sensitivity limitations of traditional NMR spectroscopy for chiral discrimination of enantiomers. Three chiral palladium pincer complexes are designed and synthesized, allowing for the recognition of various chiral analytes at low concentrations. The abundance of F-19 atoms enables the determination of enantiocomposition, even in the low micromolar range.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Xi Zou, Hanbing Wang, Bing Gao
Summary: A novel copper-catalyzed cross-coupling reaction has been developed for the synthesis of optically pure sulfoximines with broad scope and functional group tolerance, demonstrating its utility in asymmetric synthesis of pharmaceutical intermediates.
Article
Chemistry, Organic
Guangxing Gu, Yue Yue, Chenyang Wang, Wei Zhang, Jian Wu, Ya Li, Yanchuan Zhao
Summary: This study introduces a F-19-labeled cyclopalladium probe for the rapid discrimination of chiral nitriles in pharmaceuticals, natural products, and agrochemicals. The probe binds reversibly to chiral nitriles, producing distinct F-19 nuclear magnetic resonance signals for each enantiomer, facilitating quick determination of enantiocomposition. The method enables simultaneous detection of seven pairs of enantiomeric nitriles and can be applied to assess the enantiomeric excess of an asymmetric C-H cyanation reaction.
Article
Multidisciplinary Sciences
Xing Wu, Wenbo Zhang, Guangwu Sun, Xi Zou, Xiaoru Sang, Yongmin He, Bing Gao
Summary: In this study, a general platform was disclosed to convert sulfonyl and sulfonimidoyl fluorides to S(VI) radicals through cooperative organosuperbase activation and photoredox catalysis. This method provides a mild and efficient approach to obtain vinyl sulfones and sulfoximines with excellent E selectivity and demonstrates its synthetic utility in the preparation of functional polymers and dyes.
NATURE COMMUNICATIONS
(2023)