Re-Inventing Olefin Oxidation Using Visible-Light Photocatalysis

利用可见光光催化重新发明烯烃氧化

• 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

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.

烯烃是容易从石油和植物生物质中获得的原料，在高价值材料的制备中起着不可或缺的作用。特别是，氧化反应用于在烯烃碳原子之间引入氧原子，从而将这些分子转化为广泛的合成中间体，如醛，酮，醇和羧酸。烯烃氧化通常使用臭氧分解反应进行，该反应主要用于大规模化学工业，在结构简单的材料上进行安全和大规模的工艺是可能的。精细化学品行业（制药和农用化学品行业）不使用这种反应性，因为它们的底物很复杂，含有脆弱的官能团。这意味着仍然需要多步骤方法来克服这一综合挑战。发明一种能够实现烯烃结构单元的一般性和选择性氧化的新化学策略对于促进和简化对我们的社会至关重要的分子的鉴定和制备具有战略重要性。该提议的总体目标是开发第一个可见光介导的光化学反应的例子，该反应能够使烯烃结构单元氧化裂解以产生醛和酮。通过这种方式，我们将提供一种独特的反应，能够简化目前难以制备但受到制药和农业化学品发现计划高度追捧的含O片段的合成。我们的目标是使用简单的硝基芳烃，一个大类的原料每年生产的多吨规模，作为光活性氧化剂结合可见光和光催化剂。该策略将探索硝基芳烃通过直接能量转移进行光激发到其三重态的能力。然后这些物种将与烯烃进行新型自由基[3+2]型环加成反应，得到一类新的杂环。通过该反应形成的物质可以有效地被认为是N-掺杂的臭氧化物，并且将经历跨C-C键的快速裂解，从而导致氧化的材料。我们将进行详细的机理研究，以充分了解活化过程以及三硝基芳烃的反应性。然后，我们将基准这种反应性，以实现逐步更复杂和功能化的烯烃结构单元的氧化。我们的目标是制备一个大型的硝基芳烃库，以评估其三重态反应性。这可能使得能够识别能够基于空间或电子因素选择性区分烯烃的试剂。 总的来说，该项目将为烯烃的快速、选择性和温和氧化开发一种创新策略。获得这些高价值材料的可能性将促进治疗剂和农用化学品的发现、开发和制造，对英国社会的福祉产生全面影响。

项目成果

Olefin Dihydroxylation Using Nitroarenes as Photoresponsive Oxidants.

• DOI: 10.1002/anie.202214508
• 发表时间: 2023-02-13
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Hampton, Charlotte;Simonetti, Marco;Leonori, Daniele
• 通讯作者: Leonori, Daniele

Olefin-Dihydroxylierung mit Nitroarenen als Photosensibilisatoren

带有硝基芳烃的烯烃二羟基光敏剂

• DOI: 10.1002/ange.202214508
• 发表时间: 2023
• 期刊: Angewandte Chemie
• 作者: Hampton C