【作者】 陈万里；

【导师】 黄宪；

【作者基本信息】 浙江大学 ， 有机化学， 2005， 博士

【摘要】 亚烃基环丙烷是一类具有高度环张力的化合物。正因为具有高度环张力,使得它具有活泼而独特的反应性能。研究亚烃基环丙烷在有机合成中应用,是一个有意义也有挑战的课题。全文分为五个部分。 一、研究了亚烃基环丙基羧酸酯与酚(硫酚、硒酚)的Michael加成,酰化串联反应,提供了一种新的4H-苯并吡喃-4-酮,4H-苯并硫代(硒代)吡喃-4-酮合成方法。 二、研究了2-溴-2-亚甲基环丙基羧酸酯与硒代酰胺的Michael加成,亲核取代串联反应,合成了一种螺环丙基取代的硒唑啉化合物,并进一步研究了三元环的开环反应。 三、研究了酸性条件下亚烃基环丙烷与腈的Ritter反应,提供了一种一锅法合成N-[(E)-高烯丙基肉桂]酰胺的新方法。 四、研究了卤化铜作用下亚烃基环丙烷的双卤化反应,提供了一种合成Z-2,4-二卤代-1-丁烯的新方法,并进一步研究了Z-2,4-二卤代-1-丁烯在合成中的应用。 五、研究了硝酸铈铵作用下亚烃基环丙烷和活性亚甲基化合物的[3+2]环加成反应,合成了一种新型的螺环丙基化合物。进一步研究了硝酸铈铵作用下亚烃基环丙烷的氧化重排生成环丁酮化合物。更多还原

【Abstract】 Methylenecyclopropanes (MCPs), which are highly strained but readily available molecules and of syiithetic interest due to the attractive feature of MCPs which have multiple possibilities for reaction of the three strained bonds (two proximal and one distal bonds) in the cyclopropane ring, have been studied.Firstly, the tandem Michael addition-intramolecular acylation of phenols, thiophenols, selenophenols with alkylidenecyclopropyl carboxylic esters was investigated and 4H-l-benzopynin - 4 - ones, 4H-l-benzothiopyran-4-ones, 4H-1-benzoselenopyran - 4 - ones were obtained respectively in moderate yields.Secondly, the tandem Michael addition-intramolecular substitution of selenoamide with 2-bromo-2-cyclopropylideneacetate was investigated and 5-spirocyclopropane-annulated selenazoline-4-carboxylates were synthesized in good yields. By the CuBr2-mediated halogenation reaction, the cyclopropyl group could be opened and two different bromines could be introduced in the molecular. The two different bromines could be further transformed.Thirdly, the Ritter reaction of alkylidenecyclopropanes was investigated and N-[(E)-hornocinnamyl] amides were stereoselectively synthesized in moderate yields in one-pot manner.Fourthly, CuX2-mediated halogenation reaction of alkylidenecyclopropanes afforded Z-2, 4-dihalobutenes highly efficiently and stereoselectively in good yields. Furthermore, Z-2, 4-dihalobutenes could be further transformed and used in the preparation of 4-alkylidene-5, 6-dihydro-4H-pyrrolo[l,2-c][l,2,3]triazoles.Finally, we developed a novel CAN-mediated radical transformation of MCPs with 1,3-dicarbonyl compounds to give the novel [3+2] annulation compounds in moderate to good yields under mild conditions. Furthermore, CAN-mediated ring-rearrangement reaction of MCPs was investigated and cyclobutanone derivatives could be obtained in moderate yields. And a preliminary study of reaction mechanism was carried out.更多还原