【作者】 刘卫敏；

【导师】 陶京朝；

【作者基本信息】 郑州大学 ， 有机化学， 2005， 硕士

【摘要】 本论文以廉价、易得的反式-4-羟基-L-脯氨酸为原料,合成了两种长链烷基醚化脯氨酸衍生物1a、1b。分别研究了化合物1a、1b在有机相和水相中对取代苯甲醛与丙酮的Aldol反应的催化活性和对映选择性。初步探讨了长链脯氨酸胺化衍生物的合成。 Ⅰ.设计了两条合成路线,以廉价、易得的反式-4-羟基L-脯氨酸为原料,合成了反式-长链烷氧基-L-脯氨酸衍生物1a、1b,并通过IR、¹HNMR、¹³cNNIR、HRMS等手段,对8种未见文献报道的中间产物和两个目标产物的结构进行了表征。培养了化合物1b的单晶并测定了其晶体结构,结果表明长链烷基取代脯氨酸衍生物具有很强的两亲性能。 路线一:更多还原

【Abstract】 In this thesis, two long-chain alliyl proline derivatives 1a and 1b were synthesized from readily available trans-4-hydroxy-L-proline. The catalytic activity and enantioselectivety of la and lb in the Aldol condensation of aromatic aldehydes and acetone were studied in organic phase or aqueous phase. Synthesis of long-chain aminated proline derivatives was preliminary studied.Ⅰ. Two long-chain alkyl proline derivatives 1a and 1b were synthesized from readily available trans-4-hydroxy-L-proline through the two synthetic routes. All eight kinds of novel intermediate products and two targete products were characterized respectively by IR, ¹HNMR, ¹³CNMR, HRMS, etc. Compound 1b was further characterized by X-ray diffraction.One:Ⅱ. Synthesis of long-chain aminated proline derivatives was preliminary studied. But the rate of conversion was very low in the process of amination. The searches of the optimal conditions of the amination and the study of their catalytic behavior for Aldol reaction are now underway.HO.Ⅲ. The catalytic activity and enantioselectivety of la in the Aldol reaction have been studied in organic phase in the influence of different solvent, temperature and the amount of catalyst etc. The results indicated that when only 3mol% of la was used , both the activities and selectivities were similar to 20mol% of la in acetone（The amount ofL-proline is about 20mol% in DMSO in the literature）. The enantioselectivity of the reaction in organic solvents is normally increased at lower reaction temperature. The catalyst also shows expanded solvent scope.OHla, 3mol%Acetone, r. t.,24h82.4%yield, 57.2%eeIV. The catalytic activity and enantioselectivity of la in the Aldol condensation were studied in aqueous phase in the influence of temperature and the amount of catalyst. In water, both the yield and ee value of the Aldol condensation of nitro- benzaldehydes and acetone were about 50%. The catalytic activity and enantio- selectivity of la was strongly dependent upon the reaction temperature and the amount of the catalyst. A plausible mechanism for the catalyzation in water was proposed and discussed. The long-chain alkyl derivatives of L-proline may form some kindes of chiral micelle systems in water by its self aggragation, by which the Aldol reaction were accelerated on the interface of the micelle through a mutual effect.OH20mol%la 63.9%yield, 44. l%ee 10 mol%la 53.4%yield, 54.5%ee 5 mol%la 46.2%yield, 62.4%ee更多还原