首页> 外文OA文献 >Active Template Strategies for the Assembly of Mechanically Interlocked Molecules
【2h】

Active Template Strategies for the Assembly of Mechanically Interlocked Molecules

机译:机械连锁分子组装的主动模板策略

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。

摘要

Chemical templates have allowed the synthesis of increasingly complexudmechanically interlocked molecular architectures. Transition metals are usefuludtemplating agents. Their coordination requirements result in the well-defined, threedimensionaludorientation of reactive fragments. Judicious choice of ligand and metaludleads to a mechanically interlocked product upon covalent bond formation betweenudthe fragments. In such ‘passive’ templates a stoichiometric quantity of metal, withudrespect to the reacting components, is required. The metal atom acts as ‘glue’ untiludcovalent, and consequent mechanical, bond formation has occurred. Recently in theudLeigh group a fundamentally novel approach to interlocked architectures has beenuddiscovered and takes its cue from transition metal catalysis: in addition to inducingudthe necessary degree of preorganization in the system, the metal also mediates theudcovalent bond formation. This thesis describes further investigation of the originaludactive template reaction—a ‘click’ reaction—and the subsequent extension of theudstrategy to new reactions and architectures.udThe effect of varying the macrocyclic ligand on the original Cu(I)-catalyzed 1,3-uddipolar cycloaddition between alkynes and azides was investigated. Notably, theudinterlocked nature of the products provided new mechanistic insights into the natureudof this widely used reaction. Following this, a Ni(II) active template was developedudfor the homocoupling of terminal alkynes. An unusual Ni/Cu system for this reactionudwas discovered and the resulting [2]rotaxanes were produced in excellent yield. Theudutility of the active template strategy was further demonstrated by the synthesis of aud[3]rotaxane from a bifurcated macrocycle with a pyridyl bridging unit. Cu(I)udcatalyzed the formation of a triazole thread through each cavity, showing thatudmultiple mechanical bonds can be formed from a single active template binding site.udLastly, the potential of carbene transfer reactions in the active template approach wasudinvestigated. A stoppered diazoester compound was synthesized and used in studiesudtowards X-H insertion and cycloaddition reactions in the presence of a range ofudmacrocyclic ligands
机译:化学模板允许合成日益复杂的 /机械耦合的分子结构。过渡金属是有用的模板剂。它们的配位要求导致了反应性碎片的明确定义的三维取向。配体和金属的明智选择会导致在片段之间形成共价键后形成机械互锁的产物。在此类“被动”模板中,需要化学计量的金属,不考虑反应组分。直到 udcovalent为止,金属原子才起着“胶水”的作用,因此形成了机械键。最近,在udLeigh小组中,人们发现了一种根本上新颖的互锁结构方法,并从过渡金属催化中获得了线索:除了在系统中诱导必要的预组织程度外,金属还介导了 udcovalent键的形成。本文描述了对原始惰性模板反应(“点击”反应)的进一步研究,以及随后的策略扩展到新的反应和体系结构。 ud改变大环配体对原始Cu(I)催化的影响研究了炔烃与叠氮化物之间的1,3- 偶极环加成反应。值得注意的是,产品的“联锁”性质为这种广泛使用的反应的性质提供了新的机械原理。此后,开发了Ni(II)活性模板,用于末端炔烃的均相偶联。发现了用于该反应的不寻常的Ni / Cu体系,并且以优异的产率制备了所得的[2]轮烷。通过从具有吡啶基桥连单元的分叉大环中合成α[ud [3]轮烷,进一步证明了活性模板策略的有用性。 Cu(I)催化通过每个腔形成三唑线,表明可以从单个活性模板结合位点形成多个机械键。 ud最后,研究了活性模板方法中卡宾转移反应的潜力 。合成了一种封端的重氮酸酯化合物,并用于研究在存在一定范围的 udmacrocyclic配体的情况下进行X-H插入和环加成反应

著录项

  • 作者

    Ronaldson Vicki E;

  • 作者单位
  • 年度 2009
  • 总页数
  • 原文格式 PDF
  • 正文语种 {"code":"en","name":"English","id":9}
  • 中图分类

相似文献

  • 外文文献
  • 中文文献
  • 专利

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