布朗斯特酸催化下邻羟基（巯基）苄醇参与的环化反应

发布时间：2018-06-08 18:56

本文选题：布朗斯特酸催化 + 邻亚甲基苯醌　；参考：《江苏师范大学》2017年硕士论文

【摘要】：第一章,从邻亚甲基苯醌中间体参与的外消旋反应和邻亚甲基苯醌中间体参与的不对称反应这两个方面,介绍了邻亚甲基苯醌中间体的研究现状。同时,介绍了本论文的研究目标和内容。第二章,我们实现了由邻羟基苄醇原位生成的邻亚甲基苯醌参与的反电子需求的催化不对称氧杂D-A反应。利用3-甲基-2-吲哚烯作为亲双烯体,高产率、高对映选择性地构建了具有3个相邻手性中心的氧杂二氢吡喃骨架(最高达到99%的产率,95:5的dr值,99.5:0.5的er值)。无论是采用邻羟基苄醇作为双烯体的前体与3-甲基-2-吲哚烯这种亲双烯体反应,还是通过氢键活化模式来活化这两种底物,都解决了反电子需求的催化不对称氧杂D-A反应中存在的挑战性问题。第三章,我们实现了邻羟基苄醇与达米酮衍生的烯胺酮类化合物的化学选择性、E/Z选择性和对映选择性的催化不对称环化反应,该反应不仅实现了烯胺酮类化合物化学选择性的环化反应,而且通过催化不对称的方法,获得了高对映选择性的、在生物学上具有重要意义的四氢氧杂蒽骨架(产物的E/Z选择性95:5,产物最高达到98%的产率,97:3的er值)。这种方法不仅是第一例达米酮衍生的烯胺酮类化合物的C1,C2位与邻羟基苄醇的催化不对称环化反应,而且为构建光学纯的含氧杂环骨架提供了一个有效的策略。第四章,我们实现了布朗斯特酸催化下邻巯基苄醇和3-烷基-2-吲哚烯或苯乙烯的[5+2]环化反应或羟基巯基化反应,这种方法可以有效地构建苯并七元含氧含硫杂环骨架,以良好的收率和高的非对映选择性合成β-羟基硫化物。
[Abstract]:In the first chapter, the research status of o-methylene benzoquinone intermediates is introduced from the two aspects of racemic reaction and asymmetric reaction in which the intermediate of o-methylene benzoquinone is involved. At the same time, the research goal and content of this paper are introduced. In chapter 2, we have realized the asymmetric oxygen hetero-D-A reaction involving the antielectronic demand of o-methylene benzoquinone, which is in situ generated from o-hydroxybenzyl alcohol. With high yield and high enantioselectivity, 3-methyl-2-indolene was used as diene hydrophilic agent to construct oxa-dihydropyran skeleton with three adjacent chiral centers (up to 99% yield of 95: 5) and er value of 99.5: 0.5. Whether it uses o-hydroxybenzyl alcohol as the precursor of dienes to react with 3-methyl-2-indolene, a dienophile, or it activates the two substrates by hydrogen bond activation mode. Both of them solve the challenging problem of catalytic asymmetric oxygen hetero-D-A reaction with anti-electron requirement. In chapter 3, we have realized the chemoselectivity and enantioselectivity catalytic asymmetric cyclization of enamines derived from o-hydroxybenzyl alcohol and damikone. This reaction not only realizes the chemoselective cyclization of enamine ketones, but also obtains high enantioselectivity by the method of catalytic asymmetry. The biologically important tetrahydrooxanthracene skeleton (the E / Z selectivity of the product is 95: 5, the highest yield of the product is 98%), the er value of the product is 97: 3. This method is not only the catalytic asymmetric cyclization of the C _ (1) C _ (2) site of the first damikon-derived enamine ketone with o-hydroxybenzyl alcohol, but also provides an effective strategy for the construction of an optically pure oxygen-containing heterocyclic skeleton. In chapter 4, we have realized [52] cyclization or hydroxyl mercaptoylation of o-mercaptobenzol and 3-alkyl-2-indolene or styrene catalyzed by Brownstearic acid. 尾-hydroxy sulfide was synthesized with good yield and high enantioselectivity.
【学位授予单位】：江苏师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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