| Active cyclic imines and aziridines are important intermediates to synthesis chiral nitrogen-containing heterocycles,and the synthetic transformation and applications of these componds have been a focused topic for organic chemistry.The nucleophilic addition reaction of indole,enol silicon ether and aryl boronic acid to aldimine have been researched widely and deeply.However,the catalytic asymmetric reaction of ketimine,which is relatively less active is few.In this dissertation,the catalytic asymmetric addition reaction of active cyclic ketimine to nucleophiles has been developed.Then,the addition reaction and the asymmetric hydrogenolysis reaction of cyclic amino-hemiaminal or amino-hemiketal which used as the precursors of imine have been developed,too.Besides,a new type of asymmetric Friedel-Crafts alkylation reaction of N-sulfonylaziridines with indoles has been developed via a kinetic resolution process.1.The enantioselective Mukaiyama-Mannich reaction of rich electronic furan or pyrrole with cyclic N-sulfonyl ?-ketiminoesters was developed in chapter 2.The asymmetric reaction which was developed by using chiral Lewis acid catalyst to active the ketiminoester substrates,constructed a tertiary carbon chiral center.After the systematic optimization of ligand,solvent,temperature and so on,the optimal condition was as follows: the complex of Ni(ClO)4.6H2O(10 mol%)-bisoxazoline(12 mol%)as catalyst,the reaction of rich electronic furan or pyrrole with cyclic N-sulfonyl ?-ketiminoesters procced effectively in toluene at-50 oC,affording 16 products in good yield(up to 99%)and excellent enantioselectivity(up to 97% ee)and moderate diastereoselectivity(up to 9:1).2.The enantioselective Mannich reaction of 3-Substituted-2-indoline with cyclic N-sulfonyl ?-ketiminoesters was developed in chapter 3.By using chiral Lewis acid catalyst to active the ketiminoester substrates,the asymmetric reaction was developed to construct vicinal quaternary stereogenic centers.After the systematic optimizations of ligand,solvent,Lewis acid,additive,temperature and so on,the optimal cocdition was defined as: the complex of Ni(ClO)4.6H2O(10 mol%)-bisoxazoline(12 mol%)as catalyst,the Mannich reaction of indolone with cyclic N-sulfonyl ?-ketiminoesters procced effectively in DCM and dioxane(1:1)at 80 oC,affording 13 products with good yield(up to 95%)and excellent enantioselectivity(up to 95% ee)and moderate diastereoselectivity(up to 5.7:1).3.By using the complex of Iridium and bisphosphine ligand as catalyst,the enantioselective hydrogenolysis reaction of 3-hydroxy-3-aryl-isoindolin-1-one was developed in chapter 4.After the systematic optimizations of solvent,ligand,additive,temperature,the pressure of hydrogen and so on,the hydrogenolysis reaction of 3-hydroxy-3-aryl-isoindolin-1-one procced effectively by using the in-situ complex of [Ir(cod)Cl]2(1.5 mol%)and(R)-MeO-Biphep(3.3 mol%)as catalyst in CHCl3 at rt,and 13 cyclic diaryl methylamine products were afforded with good yield(65-99%)and moderate to good enantioselectivity(53-86% ee).4.The Friedel-Crafts type reaction of 3-hydroxy-isoindolin-1-one with alkene was developed in chapter 5.After the systematic optimization of Lewis acid,solvent,temperature and the amount of catalyst,the Friedel-Crafts type reaction of 3-hydroxy-isoindolin-1-one with alkene was achieved by using Cu(OTf)2(2 mol%)as catalyst,and 18 cyclic allylic amides were afforded with excellent yield(30-99%).Besides,a preliminary result(16% ee)was got by using chiral phosphamide as catalyst.5.A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines was developed in chapter 5.After the systematic optimization of ligand,solvent,temperature Lesis acid and so on,the asymmetric Friedel-Crafts reaction of indoles with N-sulfonylaziridines was achieved by using the complex of Cu(CH3CN)4BF4(10 mol%)/(S)-Segphos(12 mol%)as catalyst,and 19 chiral tryptamine derivatives were got with good yield(up to 99%)and excellent enantioselectivity(up to >99% ee). |
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