• 主题
高级搜索  >
历史搜索 清空历史
首页> 美国卫生研究院文献>BMC Chemistry >New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones
【2h】

New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

机译：用于钌催化酮的对映选择性氢化的新膦二胺和膦氨基氨基醇三齿配体以及通过不对称还原氰基酮实现的简洁内酯合成

代理获取
本网站仅为用户提供外文OA文献查询和代理获取服务，本网站没有原文。下单后我们将采用程序或人工为您竭诚获取高质量的原文，但由于OA文献来源多样且变更频繁，仍可能出现获取不到、文献不完整或与标题不符等情况，如果获取不到我们将提供退款服务。请知悉。
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S)-1-amino-2-indanol, (S,S)-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R)-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L)(DMSO)] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.
机译：酮的对映选择性氢化是有机化学中的关键反应。过去，我们尝试通过引入手性三齿膦-二胺/ Ru催化剂来应对这一领域中一些尚未解决的挑战。本文介绍了新的催化剂和新的应用，包括合成衍生自（R，S）-1-氨基-2-茚满醇，（S，S）-1-氨基-的膦-氨基醇P，N，OH配体2-茚满醇和（R，R）-1,2-二苯基乙二胺衍生的新手性P，N，N配体。分离[RuCl2（L）（DMSO）]类型的钌前催化剂，然后在酮的氢化中进行检查。尽管新的基于P，N，OH配体的催化剂较差，但新的P，N，N体系的e.e.高达98％。不会与大多数催化剂完全反应的基材上初步尝试通过在苯乙酮和丙烯腈之间进行有机催化迈克尔加成反应，然后对腈官能化的酮进行不对称加氢来实现新的三角洲内酯合成，这在一定程度上具有挑战性，部分原因是由于迈克尔加成化学反应，而且由于Noyori压力加氢催化剂大大降低了反应性相对于其他苯乙酮衍生物的性能。钌膦-二胺体系可实现定量转化，e.e。约为50％。通过用KOH处理可将产物转化为δ内酯，同时完全保留对映体过量。这种方法可以从非常便宜的构件丙烯腈和甲基酮分三步提供接近此类手性分子的途径。我们鼓励研究人员在这个可能有用但目前存在缺陷的过程中改进我们的工作。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
代理获取

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