CAREER: Understanding and Directing Selectivity in Functionalizations of Strong Covalent Bonds Utilizing Coordination-Sphere Effects

职业：利用配位球效应理解和指导强共价键官能化的选择性

• 批准号: 2338438
• 负责人: Shuming Chen
• 金额: $ 55万
• 依托单位: Oberlin College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-07-01 至 2029-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2338438&HistoricalAwards=false
• 关键词: CAREER; Understanding; Directing; Selectivity; Functionalizations

With support of the Chemical Structure, Dynamics & Mechanisms-B Program of the Chemistry Division, Shuming Chen of the Department of Chemistry and Biochemistry at Oberlin College will use computational models to help understand and steer selectivity in reactions catalyzed by transition metal-ligand complexes. These reactions can be used to transform strong covalent bonds, such as carbon-carbon and carbon-hydrogen bonds, into usefully functionalized compounds, with wide-ranging implications for catalytic chemistry in materials synthesis, natural product total synthesis and pharmaceutical drug candidate synthesis. This project will also pursue educational initiatives aimed at fostering greater involvement in scientific research for students from underrepresented backgrounds. These initiatives encompass a variety of activities, including the Seed Experience in Authentic Research for First-Years (SEARF) workshop, which offers first-year chemistry students at Oberlin a straightforward entry point into authentic research. Collaborative development of open-source pedagogical modules will address challenges associated with teaching transition-metal mechanisms in undergraduate classrooms. To further promote equitable access to scientific research, the project will also provide financial support for undergraduate students to perform research throughout the academic year and to high school students during the summer months. While mechanistic insight derived from computations is increasingly used to inform the development of new synthetic methodologies, many important transition-metal-catalyzed systems remain challenging for computationally-guided reaction design. The overarching research objective of this project is to develop and apply effective computational models to understand and predict transition-metal-catalyzed functionalizations of strong covalent bonds. Building on preliminary results that revealed multiple types of unexpected coordination-sphere effects in C–H, C–C and C=C functionalization systems, Dr. Chen and her research group plan to carry out computational studies that will shed light on the interactions between coordination-sphere elements. They aim to elucidate the power structure of coordination-sphere effects, including the primary (core ligand moieties), secondary (pendant ligand moieties), and tertiary (solvent shell) coordination spheres, in key mechanistic steps that often constitute the energetic bottlenecks of synthetically useful chemical transformations. Their efforts have the important potential to quantify these effects on measurable reaction outcomes and reveal productive directions for reaction design based upon coordination sphere effects.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学结构、动力学和机理-B项目的支持下，欧柏林学院化学与生物化学系的陈树明将使用计算模型来帮助理解和控制过渡金属-配体配合物催化反应的选择性。这些反应可用于将碳-碳和碳-氢键等强共价键转化为有用的功能化化合物，对材料中的催化化学具有广泛的影响该项目还将开展教育活动，旨在促进来自代表性不足背景的学生更多地参与科学研究，这些活动包括各种活动，包括首次真实研究的种子体验。 -Years (SEARF) 研讨会，为欧柏林大学一年级化学学生提供了一个直接进入真实研究的切入点，合作开发开源教学模块将解决与本科生课堂教学过渡金属机制相关的挑战。为了进一步促进公平的科学研究机会，该项目还将为本科生在整个学年进行研究以及为高中生在夏季进行研究提供财政支持，同时从计算中获得的机械洞察力越来越多地用于为科学研究的发展提供信息。尽管新的合成方法，许多重要的过渡金属催化系统对于计算引导的反应设计仍然具有挑战性，该项目的总体研究目标是开发和应用有效的计算模型来理解和预测强共价的过渡金属催化官能化。初步结果揭示了 C-H、C-C 和 C=C 官能化系统中多种类型的意外配位层效应，陈博士和她的研究小组计划开展计算研究，以阐明这些键。他们的目的是阐明配位层效应的动力结构，包括关键机制中的初级（核心配体部分）、次级（侧配体部分）和三级（溶剂壳）配位层。这些步骤通常构成合成有用的化学转化的能量瓶颈，他们的努力具有重要的潜力，可以量化这些对可测量反应结果的影响，并揭示基于配位圈效应的反应设计的生产方向。该奖项反映了 NSF 的法定使命，并被视为值得通过使用基金会的智力优点和更广泛的影响审查标准进行评估来支持。