Stereospecific arylation of organolithiums: synthetic, mechanistic and structural investigation

有机锂的立体定向芳基化：合成、机理和结构研究

• 批准号: EP/F069103/1
• 负责人: Jonathan Clayden
• 金额: $ 39.21万
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2009
• 资助国家: 英国
• 起止时间: 2009 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FF069103%2F1
• 关键词: Stereospecific; arylation; organolithiums; synthetic; mechanistic

The discovery of new small molecules for use as drugs, agrochemicals, fragrances etc. relies on the availability of simple precursors that can be incorporated into more complex target molecules. The research we propose will lead to a simple and efficient way of making some classes of molecule currently considered difficult or even impossible to obtain, a limitation which means that some groups of potential targets are currently unavailable. It seeks to develop a transformation in which an aromatic ring becomes bonded to a lithium-bearing carbon atom in such a way that the shape of the starting material is remembered in the product. The products have the common feature of a highly hindered carbon atom carrying an O, N or S substituent - a feature difficult to construct by existing methods. The proposed reactions proceed by a remarkable mechanism, and by joint investigation involving both synthetic organic and structural inorganic chemists we propose to understand why the reaction works the way it does and to use this understanding to develop further related transformations.

用于药物、农用化学品、香料等的新的小分子的发现依赖于可以并入更复杂的靶分子的简单前体的可用性。我们提出的研究将导致一种简单有效的方法，使目前被认为难以获得甚至不可能获得的某些类别的分子，这意味着某些潜在目标目前无法获得。它试图开发一种转变，其中芳环与含锂碳原子键合，从而使起始材料的形状在产品中被记住。这些产物具有携带O、N或S取代基的高度受阻碳原子的共同特征-这是难以通过现有方法构建的特征。提出的反应进行了一个显着的机制，并通过联合调查涉及合成有机和结构无机化学家，我们建议了解为什么反应的工作方式，它并利用这种理解，以发展进一步的相关转换。

项目成果

Ligand effects in the formation of tertiary carbanions from substituted tertiary aromatic amides.

从取代的叔芳族酰胺形成叔碳负离子的配体效应。

• DOI: 10.1002/chem.201100240
• 发表时间: 2011
• 期刊: Chemistry (Weinheim an der Bergstrasse, Germany)
• 作者: Smith AC