Shining a New Light on Photoredox Catalysis and Small Molecule Activation
揭示光氧化还原催化和小分子活化的新亮点
基本信息
- 批准号:EP/V056069/1
- 负责人:
- 金额:$ 120.25万
- 依托单位:
- 依托单位国家:英国
- 项目类别:Fellowship
- 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:
- 关键词:
项目摘要
This project will provide detailed and much-needed understanding of fundamental reaction mechanisms in the emerging field of photoredox catalysis. This will be used to achieve long-sought-after but highly challenging new chemical transformations. These include the unprecedented direct conversion of inert but abundant dinitrogen directly into useful nitrogen-containing compounds, bypassing existing industrial methods that require extreme conditions, enormous energy input and inefficient, multi-step procedures.Chemical synthesis - the process by which simple and readily-available chemical precursors are transformed into progressively more complex, functional and valuable compounds - is a crucial scientific discipline and a key foundation of modern society, providing access to the almost innumerable synthetic chemicals encountered throughout every branch of industry. In recent years, one of the most dramatic and exciting developments in this area has been the emergence of so-called "photoredox catalysis" (PRC). PRC reactions use visible light as an abundant energy source to drive complex and challenging chemical reactions under very mild conditions, using easy- and safe-to-handle reagents, and with high selectivity. As a result, they are typically significantly less hazardous, less wasteful, and more sustainable than existing options. The development of this field is therefore a crucial goal of modern synthetic chemistry that promises significant improvements to the environmental impact of a wide variety of chemical processes.In order to facilitate the application of PRC methods towards these challenging goals it is essential to understand the underlying mechanisms - that is, the individual reaction steps that combine to give rise to these complex reactions - as it is this understanding that provides the framework for further progress. Unfortunately, investigations into these mechanisms are significantly underdeveloped, creating a substantial barrier to further advances. As the demands on new PRC reactions become ever more stringent (in terms of yield, selectivity, complexity and, pertinently, substrates) this problem is becoming ever more acute.This project will provide a powerful new method for investigating PRC reactions. By carefully isolating proposed intermediate states of the catalyst it will become feasible to investigate individual reaction steps in a precisely controlled manner. By directly interrogating the elementary reaction steps of the catalytic cycle it will be possible to clearly and unambiguously establish a comprehensive mechanistic picture of PRC processes. The resulting deep understanding of established catalysts and reactions will permit their rapid optimisation, alongside the development of entirely new and unprecedented transformations.As a compelling example, PRC will be used to facilitate the direct transformation of dinitrogen (N2) using mild reagents and under mild conditions. N2 is one of the single most important feedstocks for the modern chemical industry, acting as an abundant source of nitrogen atoms. However, the transformation of the highly inert N2 molecule is notoriously challenging and must currently be performed using the century-old Haber-Bosch process, which generates NH3 under extremely high temperatures and pressures and has an enormous environmental footprint (being responsible for roughly 2% of total world energy consumption). This NH3 can then be further transformed into other nitrogen-containing compounds, which typically requires multiple reaction steps, further limiting overall efficiency. In contrast, PRC methods will allow N2 activation to be performed under much milder conditions. Moreover, they will allow N2 to be transformed not only into NH3, but also directly into other useful nitrogen-containing compounds (e.g. triarylamine hole transporters used in OLEDs), thus bypassing the need for the laborious multi-step procedures needed to produce them via NH3.
该项目将提供详细的和急需了解的基本反应机制在新兴领域的光氧化还原催化。这将用于实现长期追求但极具挑战性的新化学转化。其中包括将惰性但丰富的二氮直接转化为有用的含氮化合物,这是前所未有的,绕过了现有的需要极端条件、巨大能源投入和低效的多步骤程序的工业方法。化学合成-将简单且易于获得的化学前体转化为越来越复杂的化学前体的过程,功能和有价值的化合物-是一个重要的科学学科和现代社会的关键基础,提供了几乎无数的合成化学品在工业的每一个分支遇到。近年来,该领域最引人注目和令人兴奋的发展之一是所谓的“光氧化还原催化”(PRC)的出现。PRC反应使用可见光作为丰富的能源,在非常温和的条件下驱动复杂和具有挑战性的化学反应,使用易于和安全操作的试剂,并具有高选择性。因此,它们通常比现有的选择危险性低得多,浪费少得多,而且更具可持续性。因此,这一领域的发展是现代合成化学的一个重要目标,它有望显着改善各种化学过程对环境的影响。为了促进PRC方法在这些具有挑战性的目标中的应用,了解潜在的机制是至关重要的-也就是说,各个反应步骤结合起来联合收割机产生这些复杂的反应-因为正是这种理解为进一步的进展提供了框架。不幸的是,对这些机制的调查还远远不够,对进一步的进展造成了重大障碍。随着对新的PRC反应的要求变得越来越严格(在产率、选择性、复杂性和相应的底物方面),这个问题变得越来越尖锐。通过仔细分离催化剂的建议中间状态,以精确控制的方式研究各个反应步骤将变得可行。通过直接询问催化循环的基元反应步骤,将有可能清楚明确地建立一个全面的PRC过程的机理图。通过对现有催化剂和反应的深入了解,可以快速优化催化剂和反应,并开发全新的、前所未有的转化方法。作为一个引人注目的例子,PRC将用于在温和的条件下使用温和的试剂促进二氮(N2)的直接转化。氮气是现代化学工业最重要的原料之一,是氮原子的丰富来源。然而,高度惰性的N2分子的转化是众所周知的挑战,目前必须使用具有百年历史的哈伯-博世工艺进行,该工艺在极高的温度和压力下产生NH3,并具有巨大的环境足迹(约占世界总能耗的2%)。然后,该NH3可以进一步转化为其他含氮化合物,这通常需要多个反应步骤,进一步限制了总体效率。相比之下,PRC方法将允许在温和得多的条件下进行N2活化。此外,它们将允许N2不仅转化为NH3,而且还直接转化为其他有用的含氮化合物(例如OLED中使用的三芳基胺空穴传输剂),从而绕过了通过NH3生产它们所需的费力的多步骤程序的需要。
项目成果
期刊论文数量(6)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Hydrostannylation of Red Phosphorus: A Convenient Route to Monophosphines.
- DOI:10.1002/chem.202202456
- 发表时间:2022-12-01
- 期刊:
- 影响因子:4.3
- 作者:Cammarata, Jose;Scott, Daniel J.;Wolf, Robert
- 通讯作者:Wolf, Robert
Isolation of the elusive [Ru(bipy) 3 ] + : a key intermediate in photoredox catalysis
难以捉摸的 [Ru(bipy) 3 ] 的分离:光氧化还原催化中的关键中间体
- DOI:10.1039/d3cc04375d
- 发表时间:2023
- 期刊:
- 影响因子:4.9
- 作者:Horsewill, Samuel J.;Cao, Chengyang;Dabney, Noah;Yang, Eric S.;Faulkner, Stephen;Scott, Daniel J.
- 通讯作者:Scott, Daniel J.
Recent Breakthroughs in P 4 Chemistry: Towards Practical, Direct Transformations into P 1 Compounds
P 4 化学的最新突破:迈向实用、直接转化为 P 1 化合物
- DOI:10.1002/ange.202205019
- 发表时间:2022
- 期刊:
- 影响因子:0
- 作者:Scott D
- 通讯作者:Scott D
Shining Fresh Light on Complex Photoredox Mechanisms through Isolation of Intermediate Radical Anions.
- DOI:10.1021/acscatal.3c02515
- 发表时间:2023-07-21
- 期刊:
- 影响因子:12.9
- 作者:Horsewill, Samuel J.;Hierlmeier, Gabriele;Farasat, Zahra;Barham, Joshua P.;Scott, Daniel J.
- 通讯作者:Scott, Daniel J.
Photocatalytic stannylation of white phosphorus.
- DOI:10.1039/d2cc03474c
- 发表时间:2022-08-09
- 期刊:
- 影响因子:4.9
- 作者:Till, Marion;Cammarata, Jose;Wolf, Robert;Scott, Daniel J.
- 通讯作者:Scott, Daniel J.
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Daniel Scott其他文献
Nucleocapsid specific T and B cell responses in humans after rabies vaccination.
狂犬病疫苗接种后人类核衣壳特异性 T 和 B 细胞反应。
- DOI:
- 发表时间:
1992 - 期刊:
- 影响因子:5
- 作者:
M. Herzog;M. Lafage;J. A. Montaño;Chantal Fritzell;Daniel Scott;Monique Lafon - 通讯作者:
Monique Lafon
Validating the Vitals assessment: A replication study on cognitive assessments and commercial driving risk
- DOI:
10.1016/j.jth.2024.101778 - 发表时间:
2024-03-01 - 期刊:
- 影响因子:
- 作者:
Alice Elizabeth Atkin;Daniel Scott;Anthony Singhal - 通讯作者:
Anthony Singhal
P597. Hippocampal Hyperactivity Can Be Generated by Dentate Gyrus Dysfunction During Adolescence
- DOI:
10.1016/j.biopsych.2022.02.834 - 发表时间:
2022-05-01 - 期刊:
- 影响因子:
- 作者:
Daniel Scott;Chunfeng Tan;Carol A. Tamminga - 通讯作者:
Carol A. Tamminga
842. Changes in Hippocampal Subfield Activity Contribute to Psychosis-Like Behaviors in Mice
- DOI:
10.1016/j.biopsych.2017.02.567 - 发表时间:
2017-05-15 - 期刊:
- 影响因子:
- 作者:
Daniel Scott;Carol A Tamminga - 通讯作者:
Carol A Tamminga
Preclinical pharmacology, ocular tolerability and ocular hypotensive efficacy of a novel non-peptide bradykinin mimetic small molecule.
新型非肽缓激肽模拟小分子的临床前药理学、眼部耐受性和降眼压功效。
- DOI:
- 发表时间:
2014 - 期刊:
- 影响因子:3.4
- 作者:
N. Sharif;Linya Li;Parvaneh Katoli;Shouxi Xu;J. Veltman;Byron Li;Daniel Scott;M. Wax;J. Gallar;Carmen M. Acosta;C. Belmonte - 通讯作者:
C. Belmonte
Daniel Scott的其他文献
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- 作者:
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