金属催化氧化反应.ppt

金属催化的氧化反应 2009.10.17 * CYP 450 TauD Acc. Chem. Res. 2007, 40, 522–531 the first article on the catalytic olefin epoxidation and alkane hydroxylation by a synthetic iron(III) porphyrin complex: Cat: synthetic iron(III) porphyrin complex, Fe(TPP)Cl (TPP=meso-tetraphenylporphyrin) J. Am. Chem. Soc. 1979, 101, 1032–1033. Acc. Chem. Res. 2007, 40, 522–531 Ligands that have been used in some Oxygenation Reactions: 1. C-H Oxidation A variety of catalysts (including Pt, Pd and Au complexes) and terminal oxidants(such as K2PtCl6, K2S2O8, CuCl2 and O2) have been used. Sen, A. Acc. Chem. Res. 1998, 31, 550–557. The First Catalytic Sulfoxidation of Saturated Hydrocarbons with SO2/O2 by a Vanadium Species: Cat : VO(acac)2 Possible Reaction Path for V-Catalyzed Sulfoxidation: J. Am. Chem. Soc. 2000, 122, 7390-7391 Kalyani, D.; Sanford, M. S. Org. Lett. 2005, 7, 4149–4152. Palladium-Catalyzed Oxygenation of Unactivated sp3 C-H Bonds J. Am. Chem. Soc.2004, 126, 9542–9543. Asymmetric hydroxylation of p-methoxyethylbenzene: ~ 87% ee Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628–3634. Groves, J. T.; Viski, P. J. Am. Chem. Soc. 1989, 111,8537–8538. Tetrahedron 1998, 54, 10017–10028. Chem.Commun. 1999, 1791–1792. Synthesis of 1,3-Difunctionalized Amine Derivatives through Selective C-H Bond Oxidation. J. Am. Chem. Soc. 2001, 123, 6935-6936 M. Christina White. J. AM. CHEM. SOC. 2005, 127, 6970-6971 Allylic C-H Oxidation/Vinylic C-H Arylation. M. Christina white. J. AM. CHEM. SOC. 2006, 128, 15076-15077 J. AM. CHEM. SOC. 2002, 124, 13978-13979 The current limitations of this methodology: the general requirement for large excesses of substrate relative to oxidant, (ii) modest levels of chemoselectivity (overoxidation to ketones is a common side reaction), (iii) the general requirement for an activated C-H bond within the molecule, (iv) modest levels of regioselectivity in substrates containing multiple weak C-H bonds, and (v) the inherent difficultie