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.

在化学学部化学结构、动力学与机理b项目的支持下，奥柏林学院化学与生物化学系的陈述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。这些反应可用于将强共价键（如碳-碳键和碳氢键）转化为有用的功能化化合物，对材料合成、天然产物全合成和候选药物合成的催化化学具有广泛的意义。该项目还将推行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的教育举措。这些倡议包括各种各样的活动，包括一年级真实研究的种子体验（SEARF）研讨会，它为奥柏林大学的一年级化学学生提供了一个直接进入真实研究的切入点。开源教学模块的协作开发将解决与本科课堂过渡金属机制教学相关的挑战。为了进一步促进科学研究的公平机会，该项目还将为本科生在整个学年进行研究提供资金支持，并在夏季为高中生提供资金支持。虽然从计算中获得的机理见解越来越多地用于为新合成方法的开发提供信息，但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过渡金属催化的强共价键的功能化。初步结果揭示了C - h、C - C和C=C功能化系统中多种意想不到的协调球效应，在此基础上，陈博士和她的研究小组计划开展计算研究，以阐明协调球元素之间的相互作用。他们的目标是阐明配位球效应的能量结构，包括一级（核心配体部分），二级（垂坠配体部分）和三级（溶剂壳）配位球，在关键的机制步骤中，往往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的反应结果的影响，并揭示基于配位球效应的反应设计的生产方向。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。