首页> 外文学位 >Fischer carbene complexes: Synthesis and application in organic synthesis.
【24h】

Fischer carbene complexes: Synthesis and application in organic synthesis.

机译:费歇尔卡宾配合物:合成及其在有机合成中的应用。

获取原文
获取原文并翻译 | 示例

摘要

Fischer carbene complexes are versatile intermediates for organic synthesis, but their synthesis can be challenging. Ile standard Fischer method of preparation involves addition of a hard anion to a metal carbonyl followed by alkylation of the resultant metal acylate with a reactive alkylating reagent. However, the alkylation step can be quite problematic. We developed a new method to prepare acyclic and cyclic aza, oxa, and thia substituted carbene complexes by simple protonation of vinyl ate complexes. This method solves the alkylation problem encountered in the standard Fischer synthesis. Reaction of M(CO) 5-TBF and vinylzinc chlorides, generated from deprotonation of vinyl ethers, vinyl thioethers and imines with t-butyllithium. followed by zinc-lithium exchange, forms vinyl ate complexes by adding to the metal of M(CO)5 -THF, which are then converted to the carbene complexes by protonation at the carbon or nitrogen atoms. Use of vinylzinc halides is critical for successful results, since vinyllithiums, hard Lewis bases, always add to a hard Lewis acid, a carbonyl carbon of M(CO)5-THF. Optimization of the reaction conditions led to the discovery that freshly prepared ZnCl 2 solution in THF is critical for high yields of the carbene complexes. In most cases, the yields of the carbene complexes prepared by this method are higher than those by other methods and some carbene complexes prepared by this method cannot be synthesized by other methods.; The synthesis of indolocarbazoles; containing hydrogen-bonding functionality mimicking the pharmacophore contained within bioactive indolocarbazole natural products is achieved. The indolocarbazoles are prepared via palladium catalyzed cross coupling of indoles followed by photochemical and thermal annulation reactions of chromium carbene complexes.
机译:费歇尔卡宾配合物是用于有机合成的通用中间体,但其合成可能具有挑战性。费歇尔标准的制备方法涉及向羰基金属中添加硬阴离子,然后用反应性烷基化试剂将所得的金属酰化物烷基化。然而,烷基化步骤可能是相当成问题的。我们开发了一种新的方法,可以通过简单地质子化乙烯基酯配合物来制备无环和环状的氮杂,氧杂和硫杂取代的卡宾配合物。此方法解决了标准Fischer合成中遇到的烷基化问题。 M(CO) 5 -TBF与乙烯基氯化锌的反应,该反应是由乙烯基醚,乙烯基硫醚和亚胺与叔丁基锂去质子化而产生的。然后锌-锂交换,通过向M(CO) 5 -THF的金属中添加形成乙烯基配合物,然后通过碳或氮原子的质子化将其转化为卡宾配合物。使用乙烯基锌卤化物对于获得成功的结果至关重要,因为乙烯基锂(硬路易斯碱)总是会在硬路易斯酸中添加M(CO)5 -THF的羰基碳。反应条件的优化导致发现新制备的ZnCl 2 THF溶液对于碳烯络合物的高产率至关重要。在大多数情况下,用这种方法制得的卡宾配合物的收率要高于其他方法,而且用这种方法制得的某些卡宾配合物不能用其他方法合成。吲哚并咔唑的合成;获得了具有氢键功能的,模拟生物活性吲哚并咔唑天然产物中所含药效基团的化合物。吲哚并咔唑是通过钯催化的吲哚的交叉偶联,然后进行铬卡宾配合物的光化学和热环化反应而制备的。

著录项

  • 作者

    You, Ying.;

  • 作者单位

    University of California, Los Angeles.;

  • 授予单位 University of California, Los Angeles.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 1999
  • 页码 425 p.
  • 总页数 425
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱:kefu@zhangqiaokeyan.com

京公网安备:11010802029741号 ICP备案号:京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有
  • 客服微信

  • 服务号