【作者】 王杨；

【导师】 张成路；

【作者基本信息】 辽宁师范大学 ， 有机化学， 2011， 硕士

【摘要】 本文以手性氨基酸为原料,设计合成了一类新型噁唑啉配体,主要内容包括:第一章文献综述本文在综述了手性在生产生活中的重要作用以及获得手性化合物方法的前提下,以噁唑啉配体为主线,综述了具有N, N、N, O、N, S、N, P等单噁唑啉配体和双噁唑啉配体在不对称催化领域的最新进展,以及所面临的挑战。既介绍了具有噁唑啉环的配体在不对称催化研究的最新成果,也包括了科学家们在该领域取得的出色成绩。第二章配体的合成设计本论文设计了6个新配体,研究了在较温和的条件合成配体的方法,成功优化了合成条件,对所有化合物分别采用包括1~H NMR、(13)~C NMR、COSY、DEPT 135、HMBC和HMQC等多种方法进行了结构表征,简捷高效地完成了目标配体的合成。在合成中分别经过氨基酸还原、氨基的氯乙酰基保护、与苯并咪唑偶联和噁唑啉构筑等4步反应成功实现了重要中间体5的合成,其中有2步取得了定量的收率,首次确定了重要中间的体5的绝对构型,为最终合成目标配体奠定了基础。最后以乙腈为溶剂、利用不同的溴代芳烃以及在不同的温度条件下较高产率地合成了6个新型目标配体,最高收率为87.7%。在新型配体的合成研究中,共计合成了27个化合物,其中新化合物7个,合成得到的催化产物为6个。自行设计并合成的6个配体,其中具有单噁唑啉环的5个,具有双噁唑啉环的1个,其中双噁唑啉环的配体结构具有一个C2轴。具有该类结构的配体是当今氮杂卡宾配体的研究热点。第三章催化反应在应用所设计的配体进行的催化反应研究中,选取配体分别研究了烯丙基烷基化、傅-克烷基化和迈克尔加成等三种反应。针对每种反应中分别筛选了最优配体和最优条件。其中在以1, 3-二苯基-2 -烯丙基醋酸酯作为底物的AAA反应中,配体A使得反应具有73.5%的最优收率;在以吲哚和甲酸乙酯为底物的傅-克烷基化反应中配体F使得反应既有91%的最优收率;以环己烯酮为底物的迈克尔加成反应配体能够催化反应发生。实验工作得到了较好的催化效果,说明合成的配体具有较好的催化活性和适用范围,研究工作为后续进一步的深入研究打下了坚实的基础,提供了重要的实验参考。更多还原

【Abstract】 In this paper, a new class of oxazoline ligands have been designed and synthesized and the chiral amino acids were used as starting materials. The main contents include: Chapter I: Literature ReviewFirst, chiral compands which play an important role of the production and life were reviewed in this paper. The latest progress, research results and outstanding achievements in the field in asymmetric catalysis of the oxazoline ligands which included N, N, N, O, N, S, N, P oxazoline ligands such as single-and double-oxazoline ligands were also reviewed.Chapter II Ligand Design and synthesisSix excellent ligands were designed and the synthetic methods under more moderate conditions were studied in this paper. The optimal synthetic conditions were gained. The characterization of all the compounds was successfully performed using a variety of characterization methods, including 1H NMR, 13C NMR, COSY, DEPT 135, HMBC and HMQC, etc. As a result, the target ligands were successfully afforded through simple and efficient synthetic route. In the synthesis, the reduction of amino acids, the protection of amino group using acetyl chloride which reacted with benzimidazole and the cross-coupling with oxazoline were putforword. The key intermediate 5 was successfully achieved, in which the quantitative yield were gained in two of the above steps. It is the first time to identify the absolute structure of the importand intermediates 5. Finally, six new target ligands were obtained in high yield in the solvent of acetonitrile and the different aryl bromides were used in different temperature conditions. The highest yield reached 87.7 %. In the synthesis of the new ligands, 27 compounds were successfully synthesized, of which 7 compounds were first synthesized and six catalytic products were also afforded. In the six ligands , there are five compounds with a single oxazoline ring and one compound with a double-oxazoline ring. The ligand with two-oxazoline ring has a C2 axis which was the hotspot in catalytic field. Chapter III catalytic reactionsIn the application of the designed ligands for the catalytic reaction, the ligands were used in allylic alkylation reaction, Friedel-Crafts alkylation reacton and Michael addition reaction. In the AAA reaction, when 1, 3-diphenyl-2-allyl acetate were the substrate, ligand A had the optimal yield of 73.5 %. In the Friedel-Crafts alkylation reacton, when indole and ethtyl-2-oxoacetate were the bubstrate, ligand F had the optimal yield of 91 %,. In the Michael addition reaction, ligands can reacted the reaction.更多还原