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Cast iron catalysis: New catalytic protocols for carbon-phosphorus bond synthesis

铸铁催化：碳磷键合成的新催化方案

基本信息

批准号：
EP/P024254/1
负责人：
Ruth Webster
金额：
$ 135.4万
依托单位：
University of Bath
依托单位国家：
英国
项目类别：
Fellowship
财政年份：
2017
资助国家：
英国
起止时间：
2017 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FP024254%2F1
关键词：
Cast iron catalysis New catalytic

项目摘要

The importance of catalysis cannot be underestimated; it is responsible for 35% of the world's Gross Domestic Product and is one of the key processes needed to tackle some of the world's grand challenges. For example, catalysis is a fundamental tool for the efficient preparation of modern pharmaceuticals and agrochemicals, vital for a rapidly expanding world population. Catalysis also contributes to our future energy needs by enabling new methods of energy capture, storage and release. It is essential for a sustainable future not least because of the inherent ability to make chemicals in a more environmentally benign manner, allowing chemical reactions to run faster at lower temperature making the preparation of key chemicals easier and more cost efficient. While the Platinum Group Metals dominate this landscape, development of abundant Base Metal alternatives is urgently required to maintain and advance global development.This fellowship will specifically deliver new catalytic strategies for the preparation of phosphines. Phosphorus-containing motifs are crucial to a host of manufacturing sectors where they constitute the vast majority of ligands used by the fine chemicals and pharmaceutical industries. Phosphines are excellent organocatalysts, constitute a range of biologically relevant motifs and since antiquity, have been central to the agrochemical industry. Traditional methods of making phosphines are inadequate by modern standards of innovative research; they often generate vast amounts of chemical waste and are limited in the types of chemical architectures that can be accessed both through a restricted pool of 'reactive' phosphines and by the small number of classical phosphine-tolerant reactions available to the synthetic chemist. We therefore need new and efficient methods to make phosphines that will overcome these technological barriers. I seek to develop novel catalytic protocols that are atom economic, use inexpensive phosphorus sources and/or exploit some of the simplest forms of phosphorus, using them in a new way to build up large amounts of molecular complexity from the simplest possible starting materials. In order to achieve this I will use mechanistic investigations to unravel the finer details of the catalytic cycles involved and thus inform future reaction development. By using iron, the fourth most abundant element in the earth's crust, these new processes will have sustainability built-in from first principles. The challenge is clear; few examples of using iron in this way exist. I aim to change this.The aim:-Investigate iron catalysts in atom-economic phosphine synthesis, making molecules relevant to the pharmaceutical and agrochemical industries.-Use iron catalysis for the activation and subsequent controlled delivery of the simplest phosphines.-Develop iron photocatalysis for completely novel reactivity, complementary to traditional thermal processes.

催化的重要性不容低估；它占世界国内生产总值的35%，是解决世界上一些重大挑战所需的关键过程之一。例如，催化作用是有效制备现代药品和农用化学品的基本工具，对迅速增长的世界人口至关重要。催化也有助于我们未来的能源需求，使新的方法能量捕获，存储和释放。它对可持续发展的未来至关重要，尤其是因为以更环保的方式制造化学品的固有能力，使化学反应在更低的温度下进行得更快，使关键化学品的制备更容易，成本效益更高。虽然铂族金属在这一领域占据主导地位，但为了维持和推动全球发展，迫切需要开发丰富的贱金属替代品。该奖学金将专门为磷化氢的制备提供新的催化策略。含磷基序对许多制造业至关重要，它们构成了精细化工和制药工业使用的绝大多数配体。磷化氢是优秀的有机催化剂，构成了一系列与生物相关的基序，自古以来就一直是农用化学工业的核心。传统的制造磷化氢的方法在现代创新研究标准下是不够的；它们通常会产生大量的化学废物，并且在化学结构类型方面受到限制，这些化学结构可以通过有限的“反应性”磷化氢池和合成化学家可用的少量经典磷化氢耐受反应来获取。因此，我们需要新的和有效的方法来制造磷化氢，以克服这些技术障碍。我寻求开发新的催化方案，原子经济，使用廉价的磷源和/或利用一些最简单形式的磷，使用它们以一种新的方式从最简单的起始材料建立大量的分子复杂性。为了实现这一目标，我将使用机械研究来揭示催化循环的细节，从而为未来的反应发展提供信息。通过使用铁，地壳中第四丰富的元素，这些新过程将从基本原理中获得可持续性。挑战是显而易见的；以这种方式使用铁的例子很少。我的目标是改变这一点。目的：研究铁催化剂在原子经济合成磷化氢中的作用，制备与制药和农化工业相关的分子。-使用铁催化活化和随后的控制输送最简单的磷化氢。-开发全新的铁光催化反应，以补充传统的热过程。