Octopus Manganese Porphyrin with Polyglycol Chains as a Catalyst for the β -Selective Epoxidation of Cholesterol Derivatives
Octopus Manganese Porphyrin with Polyglycol Chains as a Catalyst for the β -Selective Epoxidation of Cholesterol Derivatives
摘要
Synthesis of a novel octopus porphyrin with polyglycol chains 1a was achieved. The catalytic activity of la's manganese complex for the epoxidation of cholesterol derivatives with PhIO give a satisfactory conversion and regioselectivity.
Synthesis of a novel octopus porphyrin with polyglycol chains 1a was achieved. The catalytic activity of la's manganese complex for the epoxidation of cholesterol derivatives with PhIO give a satisfactory conversion and regioselectivity.
参考文献10
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4[4]Compound 1a: 1H-NMR (400 MHz, CDCl3, TMS) δ(ppm): 7.74 (d, 8H,J=8Hz,Ph-H), 7.33 (d, 8H, J=8Hz, Ph-H), 6.86 (s, 8H, Ph-H), 6.78 (s, 4H, Ph-H), 6.59-6.40 (m, 8H, Pyrrol-H), 5.28 (s, 8H, OCH2Ph), 3.67-3.50 (m, OCH2-, N-H), 3.37 (s, 24H, CH3O-); IR (KBr, cm-1): 3484 (NH), 2872 (CH2), 1596 (Ar-H), 1108 (C-O-C); UV/Vis (λmax, CHCl3, nm): 421(soret), 518, 555, 650.
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5[5]Synthesis of 1b:A mixture of 1a (668 mg, 0.15 mmol), Mn(OAc)2·4H2O (98 mg, 0.4 mmol) and DMF (40 mL) was refluxed for 24 h, then distilled to dryness under reduced pressure. To the residue was added dichloromethane (30 mL). The solid was filtrated off. The filtrate was washed with water (3×10 mL), dried over Na2SO4 and evaporated to dryness. The residue was chromatographed on silica gel with methanol/dichloromethane (1:10) as the eluent to get green product (466 mg), yield 69%. The content of manganese 0.18 mmol/ 1 g 1b. UV/Vis (λmax, CHCl3, nm): 481 (soret), 587, 624.
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9[9]Procedure for epoxidation of alkenes catalyzed by octopus manganese porphyrin 1b using PhIO as oxidant. A mixture of alkene (20 mg, 0.046 mmol), PhIO (12.3 mg, 0.056 mmol), and 1b (0.17 mg, 3.7×10-5 mmol) in CH2Cl2 (4 mL) were stirred at room temperature. When the reaction was completed (detected by TLC). The solid was filtrated off. The filtrate was evaporated in vacuo to remove the solvent and the residue was analyzed by 1H-NMR(400 MHz) to determine the conversion, yield and selectivity.
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10[10]J. L. Zhang, C. M. Che, Org. Lett., 2002, 4, 1911; V. K. Aggarwal, R. A. Stenson, R. V. H. Jones, R. Fieldhouse, J. Blacker, Tetrahedron. Lett., 2001, 42, 1587; M. Frohn, M. Dalkiewicz, Y. Tu, Z. X. Wang, Y. Shi, J. Org. Chem., 1998, 63, 2948; K. Kamahori, K. Ito, S. Itsuno, J. Org. Chem., 1996, 61, 8321. The calculated method of conversion, yield and selectivity was described as follow: C6-Hs of cholesterol, α-epoxide and β-epoxide have different chemical shifts in 1H-NMR, which locate at δC6-H=5.3-5.4, 2.83-2.89, and 3.06-3.08 ppm respectively. Conversion, yield and selectivity were calculated by the intensities of C6-Hs peaks in 1H-NMR.
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