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Highly efficient vanadium catalysts containing ligands based on hydroxamic acids were recently employed in the asymmetric epoxidation of allylic alcohols, see: (a) Zhang, W, Basak, A, Kosugi, Y, Hoshino, Y, Yamamoto, H. Angew. Chem. Int. Ed. 2005, 44, 4389. For selected earlier reports, see
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Highly efficient vanadium catalysts containing ligands based on hydroxamic acids were recently employed in the asymmetric epoxidation of allylic alcohols, see: (a) Zhang, W.; Basak, A.; Kosugi, Y.; Hoshino, Y.; Yamamoto, H. Angew. Chem. Int. Ed. 2005, 44, 4389. For selected earlier reports, see:
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General Procedure for the Preparation of Hydroxamic Acid Ligands 1a-d To a solution of 2,4,6-trichloro-1,3,5-triazine (0.1 mmol) in anhyd CH2Cl2 (8 mL) cooled to 0°C, the following components were added in the order they are written: Bocprotected amino acid (3 mmol, NMM (6 mmol, DMAP (0.3 mmol, and NH2OH·HCl (3 mmol, The reaction mixture was stirred at r.t. for 14 h and thereafter filtered through a plug of silica, using EtOAc as eluent. The residue obtained after evaporation of the filtrate was chromatographed on silica (EtOAc-pentane, 10:1, followed by recrystallization from acetone-pentane to give the hydroxamic acids. Compound 1a: yield 41, 1H NMR (400 MHz, acetone-d6, 25°C, δ, 10.09 (s, 1 H, 8.22 (br s, 1 H, 6.06 (s, 1 H, 4.08 (q, J, 7.11 Hz, 1 H, 1.40 (s, 9 H, 1.29 (d, J, 7.11 Hz, 3 H, 13C NMR 100 MHz, acetone-d6, 25°C
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6, 25°C): δ = 167.3, 154.7, 138.9, 128.3, 127.6, 127.0, 78.6, 55.7, 27.5.
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37049076654
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For the original report on the importance of external base in transition-metal-catalyzed transfer-hydrogenation reactions, see: Chowdhury, R. L, Bäckvall, J.-E. J. Chem. Soc, Chem. Commun. 1991, 1063
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For the original report on the importance of external base in transition-metal-catalyzed transfer-hydrogenation reactions, see: Chowdhury, R. L.; Bäckvall, J.-E. J. Chem. Soc., Chem. Commun. 1991, 1063.
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35348988368
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2] (0.0025 mmol), ligand (0.0055 mmol), and LiCl (0.05 mmol) were dried under vacuum in a dry Schlenk tube for 15 min. Ketone (1 mmol), i-PrOH (4.5 mL), and a 0.01 M solution of i-PrONa in i-PrOH (0.5 mL, 5 mol%) were added under nitrogen. The reaction mixture was stirred at ambient temperature. Aliquots were taken after the reaction times indicated in Tables 1 and 2 and were then passed through a pad of silica with EtOAc as the eluent. The resulting solutions were analyzed by GLC (CP Chirasil DEXCB).
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2] (0.0025 mmol), ligand (0.0055 mmol), and LiCl (0.05 mmol) were dried under vacuum in a dry Schlenk tube for 15 min. Ketone (1 mmol), i-PrOH (4.5 mL), and a 0.01 M solution of i-PrONa in i-PrOH (0.5 mL, 5 mol%) were added under nitrogen. The reaction mixture was stirred at ambient temperature. Aliquots were taken after the reaction times indicated in Tables 1 and 2 and were then passed through a pad of silica with EtOAc as the eluent. The resulting solutions were analyzed by GLC (CP Chirasil DEXCB).
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48
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35348951207
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Turnover frequencies determined after 30 min reaction time
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Turnover frequencies determined after 30 min reaction time.
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