SusChEM: Deoxygenation and Reductive Coupling of Alcohols Catalyzed by Oxo-Metal Complexes

在这个由化学系化学催化项目资助的项目中，俄克拉何马大学化学系的Kenneth M. Nicholas教授正在开发从醇中去除氧的方法。植物的许多成分，如纤维素和乙二醇，都是醇，将它们转化为有价值的商品往往需要除去氧气。然而，这是一个很难完成的过程。在这个项目中，正在开发铼和钒化合物作为催化剂，以一种环保的方式有效地脱氧和偶联醇。最终，该项目可能会开发新的化学工艺，将来自植物的可再生原料转化为有用的化学品和燃料。该项目为俄克拉何马大学、两所地区学院（分别位于德克萨斯州和路易斯安那州）以及俄克拉何马科学与数学学院的未来科学家提供教育和技术培训。本项目的总体目标是发现、发展和机械地阐明采用氧铼和钒催化剂和经济、良性还原剂的所有类醇的选择性脱氧反应。目标反应包括醇和酚的脱氧、醇还原偶联和1，n-二醇的还原环化。通过对底物和催化剂依赖的催化脱氧、还原偶联产物选择性、可能的金属-醇氧化合物反应中间体的反应性、氢和一氧化碳对氧-金属络合物的还原以及潜在反应途径的计算模型的研究，正在建立结构/反应性关系和对氧转移反应的机理见解。

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Kenneth M. Nicholas, Chemistry Department, University of Oklahoma, is developing methods for removing oxygen from alcohols. Many components of plants, such as cellulose and glycols, are alcohols and the conversion of these into valuable commodities often requires the removal of oxygen. However, this is a difficult process to accomplish. In this project rhenium and vanadium compounds are being developed as catalysts that effectively deoxygenate and couple alcohols in an environmentally benign way. Ultimately, the project may develop new chemical processes for the conversion of renewable feedstocks made from plants into useful chemicals and fuels. The project provides educational and technical training for future scientists at the University of Oklahoma, two regional colleges (in Texas and Louisiana), and the Oklahoma School of Science and Math.The overall objective of this project is to discover, develop and mechanistically elucidate selective deoxygenation reactions of all classes of alcohols employing oxo-rhenium and -vanadium catalysts and economical, benign reductants. The targeted reactions include alcohol and phenol deoxygenation, alcohol reductive coupling, and reductive cyclizations of 1,n-diols. Structure/reactivity relationships and mechanistic insights into oxygen-transfer reactions are being established through the study of substrate- and catalyst-dependent catalyze deoxygenation, reductive coupling product selectivity, the reactivity of probable metal-alkoxide reaction intermediates, reductions of oxo-metal complexes by hydrogen and carbon monoxide, and computational modeling of potential reaction pathways.