• 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>other >Catalytic Reductive ortho-C–H Silylation of Phenols with Traceless Versatile Acetal Directing Groups and Synthetic Applications of Dioxasilines
【2h】

Catalytic Reductive ortho-C–H Silylation of Phenols with Traceless Versatile Acetal Directing Groups and Synthetic Applications of Dioxasilines

机译：具有无痕多功能缩醛导向基团的苯酚的催化还原邻位C-H甲硅烷基化反应和二恶唑啉的合成应用

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

A new, highly selective, bond functionalization strategy, achieved via relay of two transition metal catalysts and the use of traceless acetal directing groups, has been employed to provide facile formation of C–Si bonds and concomitant functionalization of a silicon group in a single vessel. Specifically, this approach involves the relay of Ir-catalyzed hydrosilylation of inexpensive and readily available phenyl acetates, exploiting disubstituted silyl synthons to afford silyl acetals and Rh-catalyzed ortho-C–H silylation to provide dioxasilines. A subsequent nucleophilic addition to silicon removes the acetal directing groups and directly provides unmasked phenol products and, thus, useful functional groups at silicon achieved in a single vessel. This traceless acetal directing group strategy for catalytic ortho-C–H silylation of phenols was also successfully applied to preparation of multisubstituted arenes. Remarkably, a new formal α-chloroacetyl directing group has been developed that allows catalytic reductive C–H silylation of sterically hindered phenols. In particular, this new method permits access to highly versatile and nicely differentiated 1,2,3-trisubstituted arenes that are difficult to access by other catalytic routes. In addition, the resulting dioxasilines can serve as chromatographically stable halosilane equivalents, which allow not only removal of acetal directing groups but also introduce useful functional groups leading to silicon-bridged biaryls. We demonstrated that this catalytic C–H bond silylation strategy has powerful synthetic potential by creating direct applications of dioxasilines to other important transformations, examples of which include aryne chemistry, Au-catalyzed direct arylation, sequential orthogonal cross-couplings, and late-stage silylation of phenolic bioactive molecules and BINOL scaffolds.
机译：通过两个过渡金属催化剂的中继以及无痕缩醛直接基团的使用，实现了一种新的，高度选择性的键官能化策略，该方法可在单个容器中轻松形成C-Si键并同时官能化硅基。特别地，这种方法涉及廉价和容易获得的乙酸苯酯的Ir催化氢化硅烷化，利用二取代的甲硅烷基合成子提供甲硅烷基乙缩醛，以及Rh催化的邻-C-H甲硅烷基化提供二恶唑啉。随后向硅的亲核加成除去了缩醛导向基团并直接提供了未掩蔽的苯酚产物，因此，在单个容器中在硅上获得了有用的官能团。这种无痕缩醛直接基团催化苯酚的邻位C-H甲硅烷基化反应也成功地用于制备多取代的芳烃。值得注意的是，已开发出一种新的正式的α-氯乙酰基导向基团，该基团可使位阻酚催化C–H甲硅烷基化。尤其是，这种新方法可以使用高度通用性和良好区分的1,2,3-三取代的芳烃，而这些芳烃很难通过其他催化途径获得。此外，所得的二恶唑啉可以用作色谱稳定的卤代硅烷等同物，其不仅可以除去缩醛导向基团，而且可以引入有用的官能团，从而导致硅桥联的芳基。我们证明了这种催化的C–H键甲硅烷基化方法具有潜在的强大合成潜力，方法是将二氧杂苯胺直接应用于其他重要的转化反应，例如芳烃化学，金催化的直接芳基化，顺序正交交叉偶联和后期甲硅烷基化酚类生物活性分子和BINOL支架的合成。

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