【作者】 吴国峰；

【导师】 张雅文； 沈宗旋；

【作者基本信息】 苏州大学 ， 有机化学， 2008， 硕士

【摘要】 一、酶法动力学拆分制备光学活性γ-内酯研究了脂肪酶对桃醛和γ-癸内酯的水解动力学拆分反应,考察了温度、pH值、酶的用量等因素对酶催化水解拆分过程的影响。选择氯化钙-阿拉伯胶水溶液作为反应介质,使γ-内酯拆分产物取得较高的ee值。回收拆分中产生的γ-羟基酸,外消旋化后再内酯化,投入下一批反应,提高了光学活性γ-内酯的总得率。二、2-烷基-β-羰基醛的不对称氢转移动态动力学拆分通过利用[RuCl(p-cymene)](S,S)-TsDPEN为催化剂,HCOOH:Et3N = 5:2为氢源,不对称氢转移动态动力学拆分一系列2-烷基-β-羰基醛1a?1p,以较高的产率和中等的ee值合成了相应的2-烷基-β-羰基伯醇2a?2p。此反应替代了传统的aldol反应,通过非aldol反应途径制备了aldol型中间体。三、α-对甲苯磺酰基醛的不对称氢转移动态动力学拆分通过利用HCOOH:Et3N = 5:2体系为氢源,[RuCl(p-cymene)](S,S)-TsDPEN为催化剂,对映选择性还原动态动力学拆分α-对甲苯磺酰基醛10a?10n,以高选择性,高产率合成了相应的β-对甲苯磺酰基伯醇11a?11n。更多还原

【Abstract】 1. Preparation of Optically Active Lactones via Enzymatic ResolutionEnzymatic resolution of racemic gama-undecalactone and gama-decalactone has been effectively studied by means of the lipase selectively catalyzed hydrolysis reaction. The influence factors such as temperature, pH value and the amounts of the lipase were optimised. Employment of the aqueous solution of calcium chloride containing gum arabic as the reaction medium, improved the ee of the resolution product. The gama-hydroxy acid formed in the resolution was recovered, racemized, lactonized and recycled in the next run, which improved the yield of the optically active lactone.2. Dynamic Kinetic Resolution of 2-Alkyl-β-Keto Aldehydes by Using Asymmetric Transfer HydrogenationAsymmetric transfer hydrogenation of a series of 2-alkyl-β-keto aldehydes 1a?1p using HCOOH:Et3N = 5:2 as the hydrogen source and (S,S)-TsDPEN based Ru (II) catalysts via dynamic kinetic resolution procceds to synthesize corresponding 2-alkyl-β-keto primary alcohols 2a?2p with good yields and moderate ee values. These reactions offer an alternative for the preparation of aldol type intermediates by a non aldol pathway.3. Dynamic Kinetic Resolution ofα-Tosyl Aldehydes by Using Asymmetric Transfer HydrogenationEnatioselective reduction ofα-tosyl aldehydes 10a?10n using HCOOH:Et3N = 5:2 system as the hydrogen source and (S,S)-TsDPEN based Ru (II) catalysts via dynamic kinetic resolution procceds to synthesize correspondingβ-tosyl primary alcohols 11a?11n with good yields and high enatioselectivities.更多还原