【作者】 王海飞；

【导师】 许鹏飞；

【作者基本信息】 兰州大学 ， 有机化学， 2009， 博士

【摘要】 本论文主要讨论了天然产物(+)-Conagenin和(+)-Furanomycin的不对称合成及铜(Ⅰ)催化的2-亚甲基吡咯环及2-亚甲基二氢呋喃环的合成。第一章天然产物(+)-Conagenin的不对称合成介绍了(+)-Conagenin及其类似物全合成研究进展。结合本实验室在合成α-氨基酸方面的经验，我们将手性摸板三环亚胺内酯应用到天然产物(+)-Conagenin的不对称全合成之中，提出了一条简便可行，目前路线最短的方案，从三环亚胺内酯出发经4步高选择性，高产率的合成了所需的(S)-甲基-丝氨酸甲酯。第二章天然产物(+)-Furanomycin的不对称合成介绍了(+)-Furanomycin及其类似物全合成研究进展。完成了天然产物(+)-Conagenin及其类似物全合成之后，我们尝试合成另一个天然产物小分子(+)-Furanomycin，利用我们的手性摸板三环亚胺内酯与醛的反应规律，设计了一条简便合理的路线。目前以Z／E比值为44∶1得到了所需顺式α，β-不饱和醛，并且高选择性的得到aldol产物，为完成(+)-Furanomycin奠定了基础。第三章铜(Ⅰ)催化的2-亚甲基吡咯环衍生物的合成。介绍了吡咯环衍生物合成研究进展，并对该类反应进行了扩展研究。我们利用碱和铜(Ⅰ)共同催化的曼尼希、氢氨化串联反应，发展了一条有效合成2-亚甲基吡咯环的方法。此外，我们对反应历程进行了更深入的研究，提出了合理的机理。第四章铜(Ⅰ)催化的2-亚甲基二氢呋喃环衍生物的合成。在本组利用碱和铜(Ⅰ)共同催化的曼尼希、氢氨化串联反应合成2-亚甲基吡咯环的基础上，我们又成功的完成了2-亚甲基二氢呋喃环的合成。由于该方法是在室温下通过分子内炔基烷氧化反应而完成的，因此该反应的区域选择性非常好，反应速率很快，而且催化剂用量小。更多还原

【Abstract】 The thesis aims at the studies on Asymmetric synthesis of (+)-Conagenin and(+)-Furanomycin and Copper(I)-catalyzed cascade reactions for the direct synthesis of2-methylenepyrrolidinesPartⅠAsymmetric synthesis of natural product (+)-ConageninIntroduced the progress in the total synthesis of natural product (+)-Conagenin andisomers. Taking most advantage of successful methods of synthesizing or-amino acids,we applied tricyclic iminolactones into the total synthesis of natural product(+)-Conagenin and designed a short practicable route that the methyl (S)-methylserinewas synthesized starting from them for 4 steps with high diastereoslective and highyield.PartⅡAsymmetric synthesis of natural product (+)-FuranomycinIntroduced the progress in the total synthesis of natural product (+)-Conagenin andisomers. After finishing the total synthesis of natural product (+)-Conagenin, we triedto synthesis the other natural product (+)-Furanomycin. A reasonable route wasdesigned to finish it by exploiting the rule of tricyclic iminolactones and aromatic oraliphatie aldehyde. Now, we have prepared theα,β-unsaturated aldehyde(Z/E=44:1)and the aldol product in high selectivity.PartⅢCopper(I)-catalyzed cascade reactions for the direct synthesis of2-methylenepyrrolidinesIntroduced the progress in the synthesis of pyrrolidine derivatives and extended tostudy on the reaction. We have developed an efficient method for the synthesis of2-methylenepyrrolidines through base and copper(I)-catalyzed Mannich、hydroamination cascade reaction. What’s more, a rational mechanism has beenproposed by deeply studies the reaction process.PartⅣCopper(I)-catalyzed reactions for the direct synthesis of 2-methylene-dihydrofuransTaking most advantage of successful methods for the synthesis of2-methylenepyrrolidines through base and copper(I)-catalyzed Mannich、hydroamination cascade reaction, we have also developed an efficient approach forthe synthesis of 2-methylene-dihydrofurans. The reaction is believed to have a goodregioselectivity and rate with small amount of catalyst.更多还原