Photochemical Carbonylation and Hydroformylation (funded by BASF)

合成用于生产农化活性物质、医药活性物质和其他复杂有机分子的酰胺和酯是具有挑战性的，因为目前最先进的工艺需要应用高温。这往往导致选择性有限，从而导致所需产品的产量和边际较低，在某些情况下，选择性有限的反应副产物将对环境产生负面影响，甚至可能阻碍农用化学品的注册。因此，新的合成方法是可取的，它们将在较低的温度下产生酰胺和酯，并具有更好的选择性。对于工业目的，原子经济和阶梯经济工艺是可取的，因为它们可以节省资金，并通过节省分离能源来提高可持续性，并通过更好的原子经济和阶梯经济来处理副产品。此外，它们还可以使绿色和生物衍生的原材料变得顺从。一种特别吸引人的合成酰胺和酯的方法是在胺或醇的存在下通过芳基卤化物的光化学羰化反应。该反应将在低温下通过中间羧酸氯化物阶段生成酰胺或酯，因此可能具有更好的选择性。此外，从原子经济和步骤经济的角度来看，这一过程非常有吸引力。光化学的作用是在不需要加热的情况下激活药物。该反应遵循与过渡金属不同的途径，开辟了一套新的范式。CO的光催化利用对于通过经典的氢甲酰化反应生产的大宗化学品也是有吸引力的。与其使用极其昂贵的Rh基催化剂，在光化学途径H2和CO中形成醛，将应用一种新的光化学方法，该方法基于不同的机理，因此有可能提供比最先进的选择性更好的机会。金属的选择将影响催化作用，并为调整化学产品以及产率和选择性提供机会。这个项目需要对有机合成化学和有机催化有浓厚的兴趣。它将在一个由六名巴斯夫资助的光化学学生组成的跨学科和整体集群的框架内考虑光氧化还原化学的细节。

Synthesizing amides and esters for the production of agrochemical actives, pharmaceutical actives, and other complicated organic molecules is challenging, as high temperatures need to be applied in current state-of-the-art processes. This often results in limited selectivity and consequently in lower yields and margin of the desired product, in some cases the side products of reactions with limited selectivity will have a negative environmental impact and can even prevent registration of agrochemicals. Novel synthetic approaches are therefore desirable that would yield amides and esters at lower temperatures and with better selectivity. For industrial purposes atom-economic and step-economic processes are desirable, as they can save money and improve sustainability by saving energy for separation, and the disposal of side products through better atom economy and step economy. Moreover, they can make green and bio-derived raw-materials amenable. One particularly attractive way of synthesizing amides and esters is by photochemical carbonylation of aryl-halogenides in the presence of amines or alcohols. This reaction will yield the amide or ester via an intermediate carboxylic acid chloride stage at low temperature and possibly therefore with better selectivity. Moreover, this process is extremely attractive in terms of atom economy and step economy. Photochemistry serves at activating the reatents without the need of putting in heat. The reaction follows a different pathway than the transition metal and opens up a new set of paradigms. Photocatalytic utilization of CO will also be attractive for bulk chemicals produced via classical hydroformylation. Rather than using extremely expensive Rh-based catalysts, in the photochemical pathway H2 and CO to form an aldehyde, a novel, photochemical method will be applied that is based on a different mechanism and therefore has the potential of offering opportunities with regard to selectivity over the state-of-the art. The selection of the metal will affect catalysis and offer an opportunity for tuning the chemical product as well as yield and selectivity. This project will require a vivid interest in organic synthetic chemistry and organocatalysis. It will consider the specifics of photo-redox-chemistry in the framework of an interdisciplinary and holistic cluster of six BASF-funded students on photochemistry.