Enantioselective and stereodivergent hydromonofluoroalkylation of conjugated and remote dienes |
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| Affiliation: | 1. College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, China;2. CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai 200032, China;3. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China;1. College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China;2. Key Laboratory of Chemical Biology of Fujian Province, State Key Laboratory of Physical Chemistry of Solid Surfaces, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China;3. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;1. State Key Laboratory of Bioactive Substance and Function of Natural Medicines, CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs, NHC Key Laboratory of Biosynthesis of Natural Products, and Beijing Key Laboratory of Non-Clinical Drug Metabolism and PK/PD Study, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China;2. Zhejiang Provincial Engineering Technology Research Center of Marine Biomedical Products, School of Food Science and Pharmaceutics, Zhejiang Ocean University, Zhoushan 316022, China;1. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China;2. Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou, 310030, China;3. Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou, 310024, China;1. School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, China;2. Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Pharmacy, Changzhou University, Changzhou 213164, China;1. Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, China;2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;3. School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130012, China |
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| Abstract: | Because of the widespread applications of optically active alkyl fluorides in medicinal and agro chemicals, enantioselective and even stereodivergent construction of alkyl fluorides remains highly desirable but underdeveloped. Transition-metal-catalyzed asymmetric hydrofluoroalkylation of readily available dienes represents a novel route to achieve this goal, yet receives scarce study. Here we report an intriguing palladium-catalyzed enantioselective hydromonofluoroalkylation reaction of conjugated dienes. Both monosubstituted and internal dienes proceed well with the transformation and furnish alkyl fluorides in generally >80% yield and >90% ee. A stereodivergent hydromonofluoroalkylation protocol via Pd/Cu co-catalysis is also established for the access to all four stereoisomers of corresponding moieties bearing a fully-substituted F-stereogenic center and vicinal tertiary carbon center. In addition, asymmetric migratory hydromonofluoroalkylation of skipped dienes is developed to realize the direct allylic C H fluoroalkylation. A compound library of enantioenriched cyclic fluorides is thus built to highlight the transformation potential of present methodology. |
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