Metal Catalysed Decarboxylative C-C Bond Formation Reactions

金属催化脱羧 C-C 键形成反应

• 批准号: EP/I038578/1
• 负责人: Igor Larrosa
• 金额: $ 40.9万
• 依托单位: Queen Mary University of London
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2011
• 资助国家: 英国
• 起止时间: 2011 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FI038578%2F1
• 关键词: Metal; Catalysed; Decarboxylative; Bond; Formation

Organic synthesis has undeniably made tremendous progress over the past two centuries. Nevertheless, our ability to efficiently synthesise molecules is mostly limited to targets of low structural complexity. Preparing more sophisticated compounds is currently possible; however, their syntheses are highly inefficient: they usually involve a high number of reaction and purification steps, with a consequent increase in waste generation, and a dramatic reduction in overall yields. Consequently, these syntheses are generally not applicable to the sustained production of complex molecules of interest. This observation has led to a general consensus in the scientific community as to the urgent need for new chemical processes supporting the development of a "greener" and more sustainable chemical industry.Traditional synthetic strategies require the presence of reactive functional groups that are used as handles for further functionalisation. This requirement is one of the factors dramatically enhancing the difficulty of syntheses. In addition, often these 'handles' are not part of the final molecule and are lost as waste by-product that may be toxic and needs to be separated and dealt with. The last two decades have seen the emergence of a more straightforward alternative: the direct functionalisation of C-H bonds. Through this strategy the typically inert C-H bonds, ubiquitous in organic molecules, can be activated by transition metal catalysts and subsequently functionalised. A second approach involves the use of carboxylic acids that can be activated via decarboxylation to direct very accurately the reactivity in a given molecule. In our research we want to combine both of these new types of reactivity to develop a series of methodologies that can form bonds between carbon atoms of molecules with a very limited amount of waste by-product and in an efficient manner. The development of such new transformations will impact on all applied areas, such as the synthesis of pharmaceuticals, agrochemicals and new materials, by providing cheap and easy access to molecules that are very difficult to make to date (and therefore not used commercially).

有机合成在过去的两个世纪里取得了巨大的进步。然而，我们有效合成分子的能力主要限于低结构复杂性的目标。制备更复杂的化合物目前是可能的;然而，它们的合成是非常低效的：它们通常涉及大量的反应和纯化步骤，从而增加废物的产生，并显着降低总产率。因此，这些合成通常不适用于持续生产感兴趣的复杂分子。这一发现使科学界达成了一个普遍共识，即迫切需要新的化学工艺来支持“更绿色”和更可持续的化学工业的发展。传统的合成策略需要反应性官能团的存在，这些官能团被用作进一步官能化的柄。这一要求是显著提高合成难度的因素之一。此外，这些“把手”通常不是最终分子的一部分，并且作为可能有毒的废物副产品而丢失，需要分离和处理。在过去的二十年里，出现了一种更直接的替代方法：C-H键的直接官能化。通过这种策略，在有机分子中普遍存在的典型惰性C-H键可以被过渡金属催化剂活化并随后官能化。第二种方法涉及使用可以通过脱羧作用活化的羧酸，以非常准确地指导给定分子中的反应性。在我们的研究中，我们希望将这两种新型反应性联合收割机结合起来，开发出一系列方法，这些方法可以在分子的碳原子之间形成键，同时产生非常有限的废物副产物，并且以有效的方式进行。这种新的转变的发展将影响所有应用领域，如药物、农用化学品和新材料的合成，因为它提供了廉价和容易获得迄今为止非常难以制造的分子（因此没有商业用途）。

项目成果

Salicylic acids as readily available starting materials for the synthesis of meta-substituted biaryls.

• DOI: 10.1039/c4cc09674f
• 发表时间: 2015-02
• 期刊: Chemical communications
• 影响因子: 4.9
• 作者: Junfei Luo;S. Preciado;Igor Larrosa

Ru-Catalyzed C-H Arylation of Fluoroarenes with Aryl Halides.

• DOI: 10.1021/jacs.6b01615
• 发表时间: 2016-03-16
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Simonetti M;Perry GJ;Cambeiro XC;Juliá-Hernández F;Arokianathar JN;Larrosa I
• 通讯作者: Larrosa I

Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings.

• DOI: 10.1021/jacs.7b05155
• 发表时间: 2017-08-23
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Perry GJP;Quibell JM;Panigrahi A;Larrosa I
• 通讯作者: Larrosa I