Lithiated Aza‐Heterocycles in Modern Synthesis
Lithiated Aza‐Heterocycles in Modern Synthesis
复制标题
现代合成中的锂化氮杂环
DOI：
10.1002/9783527667512.ch15
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发表时间：
2014
影响因子：
2.7
通讯作者：
C. Comoy
中科院分区：
文献类型：
--
作者：
Y. Fort;C. Comoy
功能性含氮杂芳族化合物，特别是六元杂环化合物（吡啶、二嗪、喹啉及其稠合衍生物），引起了全世界化学家的关注，因为它们在新药物、农用化学品、催化剂或包括聚合物在内的材料的开发中发挥着重要作用。除了经典反应之外，提供有机锂化合物的金属化反应也特别令人感兴趣，因为它们允许从本质上比类似的杂环更酸性的裸露或稀疏取代的杂环开始直接官能化苯环系统。随后开发了一系列方法来调整区域选择性、化学选择性，有时还有立体选择性。目标通常是控制这些额外的影响，在易受锂化作用的各个位点提供动力学或热力学酸度的变化。本章描述了有机锂工具，这些工具允许（i）直接衍生化裸露的含氮杂芳烃； (ii) 吡啶和类似物的偶极加合物的金属化； (iii) 卤素/锂交换； (iv)通过使用定向金属化基团进行环金属化； (v) 引发卤素舞的锂化； (vi) 横向和远程锂化（方案 15.1）。接下来，这些工具（通常组合使用）的有用性通过多官能衍生物的选定反应性得到证明。
Functional nitrogen‐containing heteroaromatic compounds, especially six‐ membered ones (pyridines, diazines, quinolines, and their fused derivatives), have attracted the attention of chemists worldwide because they play an important role in the development of new pharmaceuticals, agrochemicals, catalysts, or materials including polymers.Besides the classical reactions, metallation reactions providing organolithium compounds are of particular interest because they allow the direct functionalization starting from bare or sparsely substituted heterocycles intrinsically more acidic than similar benzene‐ring systems. An arsenal of methodologies has then been developed to tune the regio‐, chemio‐, and sometimes stereoselectivities. The goal is generally to control these additional influences, providing variation of kinetic or thermodynamic acidity at various sites susceptible to lithiation.This chapter describes organolithium tools that allow (i) direct derivatization of bare N‐containing heteroaromatics; (ii) metallation of dipolar adducts of pyridines and analogs; (iii) halogen/Li exchanges; (iv) ring metallation by using directing metallation groups; (v) lithiation invoking an halogen dance; and (vi) lateral and remote lithiations (Scheme 15.1). Next, the usefulness of these tools, often used in combination, is demonstrated by selected reactivities of polyfunctional derivatives.
影响因子：
5.2
作者：
Sammakia, T;Stangeland, EL;Whitcomb, MC
通讯作者：
Whitcomb, MC
影响因子：
4.9
作者：
Melzig, Laurin;Rauhut, Christian B.;Knochel, Paul
通讯作者：
Knochel, Paul