Photochemical Carbonylation and Hydroformylation (funded by BASF)

合成用于生产农用化学活性物质、药物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，因为在目前最先进的方法中需要应用高温。这通常会导致选择性有限，从而导致所需产品的产率和利润较低，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，甚至可能阻止农用化学品的注册。因此，需要新的合成方法，其将在较低温度下以更好的选择性产生酰胺和酯。出于工业目的，原子经济性和分步经济性方法是理想的，因为它们可以通过节省用于分离的能量来节省资金并提高可持续性，并且通过更好的原子经济性和分步经济性来处理副产物。此外，它们可以使绿色和生物衍生的原材料适合。合成酰胺和酯的一种特别有吸引力的方法是在胺或醇的存在下通过芳基卤化物的光化学羰基化。该反应将在低温下经由中间体羧酰氯阶段产生酰胺或酯，因此可能具有更好的选择性。此外，该方法在原子经济性和步骤经济性方面极具吸引力。光化学的作用是在不需要加热的情况下激活活性物质。该反应遵循与过渡金属不同的途径，并开辟了一套新的范式。CO的光催化利用对于通过经典加氢裂化生产的大宗化学品也将是有吸引力的。与使用极其昂贵的Rh基催化剂不同，在光化学途径中H2和CO形成醛，将应用基于不同机制的光化学方法，因此有可能提供关于选择性的机会，金属的选择将影响催化作用并提供调整化学产物以及产率和选择性的机会。这个项目将需要在有机合成化学和有机催化生动的兴趣。它将考虑光氧化还原化学的具体情况在一个跨学科和整体集群的六个BASF资助的光化学学生的框架。

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.