导　　师： 王彦广

学科专业： 070303

授予学位： 硕士

作　　者： ;

机构地区： 浙江大学

摘　　要： 分子碘具有一定的Lewis酸的特性,可以作为Lewis酸催化有机化学反应,分子碘催化的有机化学反应具有收率高、反应时间短、选择性高,反应条件温和等诸多优点因而受到有机化学界的重视,在近几年,被广泛用于催化各种有机反应,成为迄今最为活跃的研究领域之一。分子碘可以催化多种反应,例如羰基、羟基、氨基的保护和脱保护;氧化还原反应;成环反应;加成反应;取代反应;各类多组分反应等。 我们研究了分子碘作为催化剂,在四氢呋喃溶剂中,室温条件下,催化水杨醛亚胺和二氢呋喃/(DHF/)或二氢吡喃/(DHP/)的aza-Diels-Alder反应,以中等到优秀的产率合成了相应的4-氨基苯并吡喃类化合物。我们还探索研究了该反应的机理。同时,在相同反应条件下,我们也拓展了该反应,使用碘催化了水杨醛亚胺和乙烯基正丁醚的反应,并得到了相应的一对非对映异构体产物。 此外,我们研究了分子碘催化苄醇和酰胺之间的C-N键形成反应,探索了该反应的各种条件,以中等到优秀的产率得到相应的产物。在相同反应条件下,我们也拓展催化了烯丙基醇和酰胺的反应,产率优秀。同时,我们对该反应进行了探索研究,并提出了一个可能的反应机理。 Molecular iodine, used as a mild Lewis acid, has received considerable attention in organic synthesis in recent years, because of its high tolerance to water, low-cost, nontoxic nature and ready availability. The reactions catalyzed by iodine often have notable features of the procedure including mild and metal-free reaction conditions, operational simplicity, using a catalytic amount of molecular iodine, short reaction time, and excellent yields with high selectivity. Owing to numerous advantages associated with this eco-friendly element, iodine has been explored as a powerful catalyst for various organic transformations, such as protection and deprotection reactions of ketone, hydroxy group and amine; oxidation and reduction reactions; addition reactions; substituted reaction; multicomponent reactions and so on. Herein, we reported two new synthetic strategies catalyzed by molecular iodine. We have described a diastereoselective synthesis of cis-fused 4-amino -pyranobenzopyrans and 4-aminofuranobenzopyrans via a molecular iodine-catalyzed aza-Diels-Alder reaction of o-hydroxybenzaldimines with DHP and DHF. The reaction was carried out in THF at room temperature and a series of products were synthesized in good yields. Furthermore, we performed this reaction with o-hydroxybenzaldimines and vinyl ether using same procedure. The reaction gave the corresponding 2-butoxy-4-aminobenzopyran as a mixture of diastereoisomers. Besides, we explored a molecular iodine-catalyzed C-N bond formation reaction of secondary benzyl alcohol with carboamide or p-toluenesulfonamide in acetonitrile, getting the corresponding aminated products in excellent yield. We investigated this reaction and gave a proposal mechanism. To extend the scope of this methodology, the reaction of allylic alcohols with amides was also carried out, affording the products in good yields.

关 键 词： 分子碘 反应 氨基苯并吡喃 键 二级苄醇 烯丙基醇

分 类 号： [O643.32]

领　　域： [理学] [理学]