Re-Inventing Olefin Oxidation Using Visible-Light Photocatalysis

利用可见光光催化重新发明烯烃氧化

基本信息

批准号：
EP/V046799/1
负责人：
Guillaume De Bo
金额：
$ 25.79万
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：
2021
资助国家：
英国
起止时间：
2021 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FV046799%2F1
关键词：
Re Inventing Olefin Oxidation Using

项目摘要

Olefins are feedstocks readily available from petroleum and vegetable biomass with an integral role in the preparation of high-value materials. In particular, oxidation reactions are used to introduce oxygen atoms across the olefin carbons and thus convert these molecules into a broad spectrum of synthetic intermediates like aldehydes, ketones, alcohols and carboxylic acids.Olefin oxidation is generally performed using the ozonolysis reaction which is mostly adopted by the bulk chemical industry where safe and large-scale processes on structurally simple materials are possible. The fine chemical sector (pharmaceutical and agrochemical industries) do not use this reactivity as their substrates are complex and contain fragile functionalities. This means that multi-step approaches are still required to overcome this synthetic challenge. The invention of a new chemical strategy able to achieve the general and selective oxidation of olefin building blocks is of strategic importance to facilitate and streamline the identification and the preparation of molecules critical to our society.The overarching aim of this proposal is to develop the first example of a visible-light-mediated photochemical reaction enabling the oxidative cleavage of olefin building blocks to produce aldehydes and ketones. In this way, we will provide a unique reaction able to streamline the synthesis O-containing fragments currently difficult to prepare but highly sought after by pharmaceutical and agrochemical discovery programs.- We aim to use simple nitro-aromatics, a large class of feedstocks produced annually on multi ton-scale, as photoactive oxidants in combination with visible-light and a photocatalyst. This strategy will explore the ability of nitro-arenes to undergo photoexcitation to their triplet state by direct energy-transfer. These species will then engage in novel radical [3+2]-type cycloadditions with olefins to give a new class of heterocycles. The species formed by this reaction can be effectively considered as N-doped ozonides and will undergo fast cleavage across the C-C bond thus leading to the oxidised materials.- We will run detailed mechanistic studies to fully understand the activation process as well as the reactivity of triple nitro-arenes.- We will then benchmarke this reactivity to achieve the oxidation of progressively more complex and functionalised olefin building blocks. We aim to prepare a large library of nitro-aromatics to evaluate heir triplet state reactivity. This might enable the identification of reagents able to selectively discriminate between olefins based on steric or electronic factors. Overall, this project will develop an innovative strategy for the fast, selective and mild oxidation of olefins. The possibility to access these high-value materials will facilitate the discovery, development and manufacture of therapeutic agents and agrochemicals with overall impact to the well-being of UK society.

烯烃是从石油和蔬菜生物量中获得的原料，在制备高价值材料中具有不可或缺的作用。特别是，氧化反应用于在烯烃碳中引入氧原子，从而将这些分子转化为众多合成中间体（如醛，酮，醇，醇和羧酸）等合成中间体。通过散装化学工业，可以在结构上简单的材料上进行安全和大规模的过程。精细的化学部门（药物和农业化学行业）不使用这种反应性，因为它们的底物很复杂并且包含脆弱的功能。这意味着仍然需要多步进方法来克服这一合成挑战。一种新的化学策略的发明能够实现烯烃构建基块的一般和选择性氧化对于促进和简化和简化对我们社会至关重要的分子的识别和制备至关重要的战略重要性。可见光介导的光化学反应的示例，可以使烯烃的氧化裂解产生醛和酮。通过这种方式，我们将提供一种独特的反应，能够简化当前难以准备的含综合含量O的含量O片段，但受到药品和农业化学发现程序的高度追捧。-我们旨在使用简单的Nitro-Aromatics，这是生产的大型原料。每年在多吨尺度上作为光活性氧化剂与可见光和光催化剂组合。该策略将探讨硝化物通过直接能量转移对三胞胎的光激发的能力。然后，这些物种将与烯烃一起进行新的自由基[3+2] - 型环加成，以提供一类新的异环的。该反应形成的物种可以有效地将其视为N掺杂的臭氧化物，并将在C-C键上进行快速切割，从而导致氧化材料。-我们将进行详细的机械研究，以充分了解激活过程以及反应性的反应性。然后，我们将进行这种反应性，以实现逐渐复杂和功能化的烯烃构建块的氧化。我们旨在准备大型的硝基芳香族学库来评估继承人三胞胎状态反应性。这可能使能够根据空间或电子因素选择性区分烯烃的试剂鉴定。总体而言，该项目将针对烯烃的快速，选择性和轻度氧化制定创新的策略。获取这些高价值材料的可能性将有助于发现，开发和制造治疗剂和农业化学物质，对英国社会的福祉产生总体影响。