Electrocatalysis in Iodine-based Oxidations

直接利用电能诱导化学转化是一种高效、绿色的有机分子活化方式。它避免了昂贵的催化剂和配体，使化学转化，否则难以实现。由于电子诱发化学反应，避免了试剂浪费。通过利用太阳能和风能，可持续的电力变得越来越可用。氧化通常需要化学计量的末端氧化剂，并且使用这种方法已经开发了有机合成中的许多重要转化。氧化剂的电化学再循环在几种情况下是可能的。仅以催化量产生和使用高价碘化合物的成功反应的关键要求是化学计量氧化剂在底物存在下选择性制备高价碘化合物的能力。化学计量的氧化剂必须仔细选择，因为它必须不直接与底物反应，但允许碘化合物的再氧化。这可以通过仅将碘（I）水溶液泵送通过电化学微反应器并将再氧化的碘（III）物质反馈回来来实现，如催化循环的底部所示。可以调节电化学电池中的电流，使得仅发生所需的碘（I）至碘（III）的氧化而不影响底物。在该项目的第二部分，这种方法将扩展到催化生成手性碘（III）试剂的立体选择性反应。学生将建立在我们在高价碘化学以及流动电化学的经验，以解决在这个项目的挑战这个极具挑战性的项目将探索新的协同作用，采取电化学对催化，然后进一步探索电催化应用。流程方法将是成功的关键，我们将与我们的工业合作伙伴在项目的3.5年内取得重大进展。

The direct use of electrical energy to induce chemical transformations is an efficient and green activation mode of organic molecules. It avoids expensive catalysts and ligands to enable chemical transformations which are otherwise difficult to achieve. Reagent waste is avoided since electrons induce the chemical reactions. Sustainable electricity is becoming increasingly available by exploiting sun and wind energy.Oxidations typically require stoichiometric amounts of a terminal oxidant and many important transformations in organic synthesis have been developed using this approach. Electrochemical recycling of the oxidant is possible in several cases. The key requirement for a successful reaction generating and using hypervalent iodine compounds in only catalytic amounts is the ability of the stoichiometric oxidant to selectively make the hypervalent iodine compound in the presence of the substrate. The stoichiometric oxidant has to be carefully selected as it must not react directly with the substrate but allow the re-oxidation of the iodine compound. This can be achieved by pumping only the aqueous iodine(I) solution through an electrochemical microreactor and feeding back the reoxidised iodine(III) species as shown in the bottom part of the catalytic cycle. The current in the electrochemical cell can be adjusted so that only the desired iodine(I) to iodine(III) oxidation takes place without affecting the substrate. In the second part of the project, this methodology will be extended to the catalytic generation of chiral iodine(III) reagents for stereoselective reactions. The student will build on our experience in hypervalent iodine chemistry as well as flow electrochemistry to address the challenges in this projectThis highly challenging project will explore new synergies in taking electrochemistry towards catalysis and then further to explore electrocatalytic applications. Flow methodology will be key to the success and with our industrial partners we will make major advancements in the 3.5 years of the project.