铜催化1,1-二取代烯烃不对称氢硼化反应的研究

发布时间：2018-03-22 00:09

本文选题：铜催化　切入点：不对称氢硼化反应　出处：《东北师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：含有手性二芳基或芳基烷基三级碳结构单元普遍存在于大量生物活性物种或药物分子中,例如,足叶草霉素、托特罗定、H1-抗组胺剂、舍曲林、雷美替胺、萘普生,在生理活性方面,该结构起到了重要作用。同时,在大量的材料结构中也普遍存在;因此,发展高对映选择性的1,1-二取代烷烃类化合物对有机合成化学具有重要的研究价值。烯烃是工业大量易得的产品,其相应的转化也在近年来被人们进行了广泛的且深入的研究。另一方面,有机硼化合物是现代有机化学中极为重要的有机中间体,在各种C C键及C X(X=N、O)键的形成中起到了不可替代的作用。因此,发展一种从廉价易得的原料,如烯烃,出发得到一种新的、温和的构建C B键的方法,无疑具有重要的理论和实际意义。近年来,从简单的非活化烯烃为原料,在过渡金属催化条件下,通过不对称氢硼化反应,对映选择性地构建C B键受到了人们广泛的关注。但是,到目前为止,在各种金属催化剂下,仅有1,1-芳基烷基类烯烃的氢硼化反应有较多的报道。对于非活化的1,1-双芳基烯烃的不对称氢硼化反应极少。据我们所知,只有两个例子,且对映选择性不超过54%,主要原因是手性催化剂区分底物的两个相似平面具有很大挑战。因此,发展1,1-二芳基烯烃不对称的氢硼化反应是非常重要的。本论文利用廉价的金属铜盐为催化剂,以易得的联硼酸频那醇酯为硼源,在商业易得的手性双磷配体条件下,高区域及对映选择性地实现了1,1-二芳基烯烃的不对称氢硼化反应,且该反应条件也适用于1,1-芳基烷基类烯烃,为具有相当挑战性的1,1-二芳基乙烯的氢硼化反应开辟了新的途径。
[Abstract]:Tertiary carbon structural units containing chiral diaryl or aryl alkyl are commonly found in a large number of bioactive species or drug molecules, such as doxorubicin, tolterodine H1-antihistamine, sertraline, remetidine, naproxen, This structure plays an important role in physiological activity. At the same time, it also exists in a large number of material structures; therefore, The development of high enantioselectivity 1-disubstituted alkanes has important research value in organic synthesis chemistry. Olefin is a large number of readily available products in industry. On the other hand, organic boron compounds are the most important organic intermediates in modern organic chemistry. It has played an irreplaceable role in the formation of various C-C bonds and C ~ (+ +) X ~ ((+)) C ~ ((+)) bonds. Therefore, a new and mild method of constructing C / B bonds from cheap and readily available raw materials, such as olefins, has been developed. There is no doubt that it is of great theoretical and practical significance. In recent years, under the condition of transition metal catalysis, the asymmetric hydrogenation of alkenes has been carried out by using simple non-activated olefins as raw materials. Enantioselective construction of C / B bonds has attracted much attention. However, up to now, under various metal catalysts, There have been more reports on the hydroboride reactions of only 1o 1- aryl alkyl alkenes. There are very few asymmetric hydroboride reactions for the unactivated 1o 1- bis aryl alkenes. As far as we know, there are only two examples. And the enantioselectivity is no more than 54, mainly because the two similar planes of the chiral catalyst to distinguish the substrate are very challenging. It is very important to develop the asymmetric hydroboride reaction of 1 ~ (-1) -diarylolefin. In this paper, using cheap copper salt as catalyst and readily available phenolyl diborate as boron source, chiral diphosphate ligands are obtained. The asymmetric hydroboride reaction of 1o 1- diaryl olefin with high region and enantioselectivity has been realized, and the reaction conditions are also suitable for 1o 1 aryl alkyl alkenes, which opens up a new way for the challenging hydrogenation of 1 1 D aryl ethylene.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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