New Strategies for Investigating Oxidative Aliphatic Carbon-carbon Bond Cleavage Reactions

在这个由化学部化学结构、动态和机制B项目资助的项目中，犹他州立大学化学系的Lisa M. Berreau教授研究了阴离子和二价金属如何影响化学反应，从而导致与催化和生物系统相关的分子中碳-碳键的氧化裂解。这些研究的结果可能会推动有用的化学品，包括药物的制备的新方法。这些研究还提供了对酶系统如何切割碳-碳键的见解，这有助于理解生物转化。该项目位于无机化学、有机化学和生物化学的界面，非常适合培养不同教育水平和对化学许多不同领域感兴趣的学生。Berreau教授是USU化学俱乐部的指导教师，该俱乐部参与了许多涉及K-12学生的外展活动。Berreau教授还积极参与学生职业发展活动，并参与旨在吸引在科学领域代表性不足的学生的招聘活动。具体来说，金属烯酸酯配合物的合成和反应性研究正被用于阐明阴离子和二价金属如何影响烯酸酯部分中依赖氧的脂肪族碳-碳键裂解反应的反应途径。在氯二酮酸配体氧化裂解的Cu(II)/双氧反应中，阴离子对双氧活化和氧-氧键断裂的影响被定义。这种反应性是作为支持的螯合配体的配位性质和二酮酸部分的结构和电子性质的函数来探索的。研究了金属离子对二价金属酸还原酮配合物的二氧反应活性的影响，揭示了酸还原酮双加氧酶如何通过酶的金属离子含量控制氧化脂肪碳-碳键裂解的区域选择性。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Lisa M. Berreau of the Department of Chemistry at Utah State University (USU) investigates how anions and divalent metals influence chemical reactions leading to the oxidative cleavage of carbon-carbon bonds in molecules of relevance to catalysis and biological systems. Results of these studies may drive new approaches in the preparation of useful chemicals, including pharmaceuticals. These studies also provide insight into how an enzymatic system cleaves carbon-carbon bond, which helps to understand biological transformations. This project lies at the interface of inorganic, organic, and biological chemistry and is well suited for training students at all educational levels and with interests in many different areas of chemistry. Professor Berreau is the faculty advisor for the USU Chemistry Club, which is involved in numerous outreach activities involving K-12 students. Professor Berreau is also active in student career development activities and participates in recruiting activities directed at engaging students underrepresented in science. Specifically, synthetic and reactivity studies of metal enolate complexes are being used to elucidate how anions and divalent metals influence the reaction pathways of dioxygen-dependent aliphatic carbon-carbon bond cleavage reactions within the enolate moiety. Anion effects on dioxygen activation and oxygen-oxygen bond scission are being defined in Cu(II)/dioxygen reactions involving oxidative cleavage of a chlorodiketonate ligand. This reactivity is being explored as a function of the coordination properties of the supporting chelate ligand and the structure and electronic properties of the diketonate moiety. Metal ion effects on the dioxygen reactivity of divalent metal acireductone complexes are being investigated to reveal how acireductone dioxygenases control the regioselectivity of oxidative aliphatic carbon-carbon bond cleavage via the metal ion content of the enzyme.