负载有机小分子催化剂的制备及在不对称有机反应中的应用-有机化学专业论文.docxVIP

ABSTRACT In the first p町t of this work， two kinds of Proline-伽rived immobilized nanocatalysts LIA and LIB were prepared using multiwall nanotubes (MWNTs)ω the solid supports，which were acidifted by 2.6 mol.L- 1 HN03 and HN031H2S04 (11刀， ，respectively. The structures of the catalysts were characterized by in仕ared h spectroscop弘 and the loading ratios of the ligand 4巾ydroxy proline were determined through TGA. These two immobilized catalysts were applied in the asymme创c Aldol ， reaction of aromatic aldehydes with cyclohexanone ，and LIA could catalyze the reaction of 4-ni衍。benzaldehyde and cyclohexanone in high diastereoselectivity but with very low yield and enantioselectivity. LIA could be recycled by simple filtration and reused for two more times，affording the similar results. In the second part of this work，two kinds of chiral phosphoric acid catalysts， (8)侧-弘3幡-(1刑a叩ph由a剖le町ny川l协)--帽 1川， 1 (8)丁)-3弘-川[2，4，6唰t衍咐r峭i(isopro叩p川y1加)phen町yl吁]-帽μ斗1，川， 1嗣B心i讪n叩aph由y抖1 忡phos叩pho倪ri比c acid (仰S2) we阳 synthesized using (功5)-川帽1斗川， 1-b巾i帽ω2♂na阶ph伽thol 但INOL) as the starting material. The struc阳res of these two new compounds w町e characterized by IR， lHNMR and 31PN侃 SI was effective for the reaction ofN-tosyl aldimine and indole ωgive 由e desired product in high yield and moderate enantioselectivity ，while S2 could catalyze the FriedelCrafts reaction of 2，2，2-trit1uoroacetophenone and indole as well as the three component reaction of 3人5-仕imethoxylaniline ，trit1uoroacetaldehyde methyl hemiacetal and indole in high yield and moderate enantioselectivity. 岛、 SI was further immobilized on MWNTs acidified by 2.6 mol.L-1 HN03 or polyethylene glycol monomethyl ether (Mw = 1900)to give two kinds of solid chiral ‘占 phosphoric acid catalysts L2 or L3. 叽刊1咀e让ir 侃struc阳阳res were characterized 忡byIRR s叩p蚓ectrum and the loading r创t刮圳io oft伽he ligand SI in L2 w郁 determined through TGA. For the asymmetric Fr