N-Heterocyclic Carbenes as Asymmetric Organocatalysts: Reaction Development

N-杂环卡宾作为不对称有机催化剂：反应进展

• 批准号: EP/E03795X/1
• 负责人: Andrew Smith
• 金额: $ 35.57万
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE03795X%2F1
• 关键词: Heterocyclic; Carbenes; Asymmetric; Organocatalysts; Reaction

Synthetic chemistry is used for the preparation of structurally complex materials on a molecular scale. Complexity in molecules is often associated with chirality - the fundamental property of a structure that renders it non-superimposable on its mirror image. For example, your right hand is chiral because it cannot be superimposed upon its mirror image (your left hand); the right hand is called the enantiomer of the left hand. Chirality also has important consequences, as it means that a right-handed glove cannot be worn on the left hand. This concept of chirality extends to the molecular level, where molecules can exist in two forms that differ only in that the arrangement of their atoms make them mirror images; indeed the majority of biochemical processes involve the interaction of chiral molecules that can exist in non-superimposable mirror image (enantiomeric) forms. This proposal investigates the application of a simple class of chiral organic molecule, known as N-heterocyclic carbenes, for their ability to catalyse selectively the formation of a single enantiomer of a given substance. A modular approach to the design and preparation of these reactive molecules that contain the necessary function and structure to promote catalysis will be used to succeed in this area. The effect of changing the structure of the N-heterocyclic carbene upon its reactivity will also be probed, and the application of these results to asymmetric synthesis and new chemical transformations investigated.

合成化学用于在分子尺度上制备结构复杂的材料。分子的复杂性通常与手性有关--手性是一种结构的基本性质，使其在其镜像上不可重叠。例如，你的右手是手性的，因为它不能叠加在它的镜像（你的左手）上;右手被称为左手的对映体。手征也有重要的后果，因为它意味着右手手套不能戴在左手上。这种手性概念延伸到分子水平，分子可以以两种形式存在，不同之处仅在于它们的原子排列使它们成为镜像;事实上，大多数生物化学过程都涉及手性分子的相互作用，这些分子可以以不可重叠的镜像（对映体）形式存在。该提案研究了一类简单的手性有机分子（称为N-杂环卡宾）的应用，因为它们能够选择性地催化给定物质的单一对映体的形成。一个模块化的方法来设计和制备这些活性分子，含有必要的功能和结构，以促进催化作用将被用来在这一领域取得成功。改变其反应性的N-杂环卡宾的结构的影响也将被探测，并将这些结果应用于不对称合成和新的化学转化研究。

项目成果

Isothiourea-mediated asymmetric O- to C-carboxyl transfer of oxazolyl carbonates: structure-selectivity profiles and mechanistic studies.

• DOI: 10.1002/chem.201102847
• 发表时间: 2012-02
• 期刊: Chemistry
• 作者: Caroline Joannesse;C. P. Johnston;Louis C. Morrill;P. Woods;M. Kieffer;Tobias A. Nigst;H. Mayr;T. Leb

An asymmetric pericyclic cascade approach to 3-alkyl-3-aryloxindoles: generality, applications and mechanistic investigations.

3-烷基-3-芳基吲哚的不对称周环级联方法：一般性、应用和机理研究。

• DOI: 10.1039/c4ob02526a
• 发表时间: 2015
• 期刊: Organic & biomolecular chemistry
• 影响因子: 3.2
• 作者: Richmond E