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

研究氧化脂肪族碳-碳键断裂反应的新策略

• 批准号: 1664977
• 负责人: Lisa Berreau
• 金额: $ 44.42万
• 依托单位: Utah State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664977&HistoricalAwards=false
• 关键词: New; Strategies; Investigating; Oxidative; Aliphatic

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.

在化学系化学结构与动力学机制B项目资助的课题中，丽莎教授（M。犹他州州立大学（USU）化学系的Berreau研究了阴离子和二价金属如何影响化学反应，导致与催化和生物系统相关的分子中碳-碳键的氧化断裂。这些研究的结果可能会推动制备有用化学品（包括药物）的新方法。这些研究还提供了酶系统如何切割碳-碳键的见解，这有助于理解生物转化。该项目位于无机，有机和生物化学的界面，非常适合培养所有教育水平的学生，并对许多不同的化学领域感兴趣。Berreau教授是USU化学俱乐部的教师顾问，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，并参加旨在吸引科学领域代表性不足的学生的招聘活动。具体而言，金属烯醇化物络合物的合成和反应性研究被用来阐明阴离子和二价金属如何影响烯醇化物部分内的双氧依赖性脂肪族碳-碳键裂解反应的反应途径。阴离子对分子氧活化和氧-氧键断裂的影响在涉及氯二酮配体的氧化裂解的Cu（II）/分子氧反应中被定义。这种反应性正在探索作为一个功能的支持螯合配体的配位性能和二酮部分的结构和电子性质。正在研究金属离子对二价金属酸还原酮配合物的双氧反应性的影响，以揭示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族碳-碳键断裂的区域选择性。