A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions |
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| Institution: | 1. Department of Applied Chemistry, Keio University, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan;2. Department of Chemistry, Keio University, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan;1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences (CAS), Guangzhou 510640, PR China;2. CAS Key Laboratory of Renewable Energy, Guangzhou 510640, PR China;3. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, PR China;4. School of Energy Science and Engineering, University of Science and Technology of China, Guangzhou 510640, PR China;1. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China;2. MOE Engineering Center of Forestry Biomass Materials and Bioenergy, Beijing Forestry University, Beijing 100083, China;3. Beijing Engineering Research Center for Biofuels, Beijing 100084, China;1. Fujian Provincial Key Laboratory of Clean Energy Utilization and Development, Jimei University, Xiamen, 361021, PR China;2. College of Mechanical and Energy Engineering, Jimei University, Xiamen, 361021, PR China;3. Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass (Xiamen University), PR China;4. Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass, PR China;5. College of Energy, Xiamen University, Xiamen, 361102, PR China;6. National Joint Engineering Research Center for Highly-Efficient Utilization Technology of Forest Biomass Resources, Southwest Forestry University, PR China;7. College of Materials Science & Chemical Engineering, Southwest Forestry University, Kunming, 650224, PR China;1. Malaysian Institute of Chemical and Bioengineering Technology (MICET), Universiti Kuala Lumpur, Lot 1988, Taboh Naning, 78000 Alor Gajah, Malaysia;2. Department of Molecular Medicine, USF Health Byrd Alzheimer’s Research Institute, Morsani College of Medicine, University of South Florida, Tampa, FL 33612, USA;3. Biology Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia;1. Institut für Analytische Chemie, Universität Leipzig, Linnéstr. 3, D-04103 Leipzig, Germany;2. Fraunhofer-Institut für Angewandte Optik und Feinmechanik (IOF), Albert-Einstein-Str. 7, D-07745 Jena, Germany |
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| Abstract: | The reaction of (Z)-3-deoxy-3-C-(hydroxymethyl)methylene]-1,2:5,6-di-O-isopropylidene-α-D-ribo-hexo-furanose, prepared from D-glucose, with 1,1-dimethoxycyclohexane in the presence of propanoic acid at 135°C, then at 200°C, provided two Claisen rearrangement products, namely (2R,3R,4S,5S)-2,3-(isopropylidene)dioxy-5-(1R)-1,2-(isopropylidene)dioxyethyl]-4-(1S)- and (1R)-2-oxocyclohexyl]-4-vinyltetrahydrofuran in a ratio of 3.3:1. L-Selectride® reduction of the major product gave the corresponding (S)-cyclohexanol exclusively. In contrast, the Claisen rearrangement of the aforementioned allylic alcohol with 3,3-dimethoxycyclohexene proceeded with complete stereoselectivity to provide the corresponding 4-(1S)-2-oxocyclohex-3-enyl]-4-vinyltetrahydrofuran exclusively. The 1,4-conjugate additions to the thus formed cyclohexenone derivative with dimethyl and divinylcuprates proceeded with complete π-facial selection to provide the 3-methylated and 3-vinylated cyclohexanone derivatives, both in high yields. |
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