Electrochemically Driven Deoxydehydration Reactions

电化学驱动的脱氧脱水反应

• 批准号: 2440493
• 金额: --
• 依托单位: University of Bath
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2440493
• 关键词: Electrochemically; Driven; Deoxydehydration; Reactions

Context of the researchIn contrast to fossil-fuel resources, renewable feedstocks from biomass are polyoxygenated. The development ofefficient processes that reduce oxygen-rich materials into more tractable substrates is an essential component ofachieving more sustainable chemical synthesis. The catalytic deoxydehydration of vicinal diols into alkenes is anattractive strategy that removes two oxygen atoms in one-step. To date, scarce and expensive rhenium-basedcatalysts have been the most widely explored for deoxydehydration in combination with a stoichiometric reductantsuch as triphenylphosphine. More readily available vanadium catalysts are also viable for deoxydehydrationprocesses using stoichiometric reductants under harsh reaction conditions.Aims and objectivesThe aim of the project is to develop an electrochemical methodology for vanadium-catalysed deoxydehydration,under mild conditions and avoiding stoichiometric waste with water as the only by-product.Initial studies will involve the preparation of a range of oxo-vanadium(V) complexes bearing various tricoordinateligands, starting from cheap vanadium precursors using established synthetic procedures. As only limited studies onthe electrochemistry of V(V) catalysts have been reported, the electrochemical behaviour of these complexes will beinvestigated using cyclic voltammetry to correlate structural changes in the ligand with the reduction potential. Thesestudies will provide key information on the nature of the reduction process and the reversibility of electron transfer.The catalysts will then be tested in a model deoxydehydration reaction of 1-phenylethane-1,2-diol, using knowledgegained from cyclic voltammetry to aid optimisation of the proton-coupled reduction. The deoxydehydration processwill be optimised in a simple undivided cell through variation of the electrode material, electrolyte, buffer, solvent, andtemperature using ElectraSyn equipment. Once a suitable procedure has bee n developed, the scope of themethodology will be assessed through variation of the diol structure, including the use of different substitutionpatterns and incorporation of various functional groups to test the reaction selectivity. The deoxydehydration protocolcan then be applied to polyoxygenated substrates derived from biomass to generate value-added alkenes that mayact as more suitable feed stocks for the chemical industry.Potential applications and benefitsThe developed deoxydehydration methodology will allow for the reduction of vicinal diols derived from biomass togive alkenes that may be used as feed stocks for the chemical industry. Compared to previously developed methods,the process will not require the use of a stoichiometric reductant, leading to water as the only by product making it amore sustainable process. The methodology should also allow for milder reaction conditions.Relevance to the research councilThe project is funded by the Engineering and Physical Sciences Research Council Doctoral Training Partnership(EPSRC DTP). The aims of the project align with the EPSRC research themes of Manufacturing the Future andPhysical Science, with particular relevance to the research areas of catalysis, synthetic organic chemistry, andelectrochemical sciences.Role of the second supervisorThe secondary supervisor of this project is Professor Frank Marken who is an expert in electrochemistry and will beable to provide expertise on the electrochemistry involved in the project form a more fundamental perspective.

研究的背景与化石燃料资源形成鲜明对比的是，生物质的可再生原料是多氧化的。将富含氧的材料降低到更可行的底物中的效率工艺的发展是使更可持续的化学合成的重要组成部分。在烯烃中催化二醇的催化脱氧脱氧于烯烃中，是一个分步的吸收性策略，它一步一步消除了两个氧原子。迄今为止，稀缺和昂贵的基于鼻的催化剂已成为脱氧脱水的探索最广泛的，结合了化学计量的还原剂和三苯基膦。在严酷的反应条件下，使用化学计量的还原因子使用化学计量的催化剂也可以可行一系列带有各种三色质体的Oxo-vanadium（V）配合物，从廉价的钒前体开始使用既定的合成程序。由于仅报道了对V（V）催化剂的电化学的有限研究，因此将使用循环伏安法将这些复合物的电化学行为进行了对配体的结构变化与还原潜力相关联。这些疗法将提供有关还原过程性质和电子转移可逆性的关键信息。然后，将使用从环状伏安仪中知识辅助的1-苯甲烷-1,2-二醇的模型脱氧脱水反应进行测试。使用电极材料，电解质，缓冲液，溶剂，溶剂和振动使用电子设备的变化，在简单的未分离细胞中优化了脱氧脱水过程。一旦开发出适当的过程，将通过DIOL结构的变化来评估Hewosogy的范围，包括使用不同的取代图案和掺入各种官能团来测试反应选择性。然后，将脱氧脱水协议应用于从生物量中得出的多氧基质，以生成增值烯烃，这些烷烃可能是化学工业更合适的饲料库存。为化学工业的供应量和受益于开发的Deoxydehydration Methodology允许用于减少生物饲料的替代化学工业，以减少Alkenes fefer for Alkases feed Alkases。与先前开发的方法相比，该过程不需要使用化学计量的还原剂，这将导致水作为唯一使其使其可持续过程的产品。该方法还应允许较温和的反应条件。研究理事会的项目由工程和物理科学研究委员会博士培训伙伴关系（EPSRC DTP）资助。该项目的目的与EPSRC研究的主题相吻合，与催化，合成有机化学，和电气化学科学的研究领域特别相关。 看法。