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

在化学系化学结构、动力学和机理-B项目的支持下，奥伯林学院化学和生物化学系的陈淑明将使用计算模型来帮助理解和指导过渡金属-配体络合物催化反应的选择性。这些反应可用于将碳-碳键和碳氢键等强共价键转化为有用的官能化化合物，在材料合成、天然产物全合成和药物候选合成中具有广泛的催化化学意义。该项目还将推行旨在促进代表人数不足的学生更多地参与科学研究的教育举措。这些举措包括各种活动，包括第一年真实研究种子经验(SEARF)讲习班，该讲习班为奥伯林大学一年级的化学学生提供了进入真实研究的直接切入点。开放源码教学模块的合作开发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获得科学研究，该项目还将为本科生在整个学年进行研究提供资金支持，并在暑期向高中生提供资金支持。虽然从计算中获得的机械洞察力越来越多地被用于指导新的合成方法的发展，但许多重要的过渡金属催化体系对于计算指导的反应设计仍然具有挑战性。这个项目的主要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官能化。在揭示了C-H、C-C和C=C功能化系统中多种意外的配位球效应的初步结果的基础上，陈博士和她的研究小组计划进行计算研究，以揭示配位球元素之间的相互作用。它们旨在阐明配位球效应的能量结构，包括一级(核心配体部分)、二级(悬挂配体部分)和三级(溶剂壳)配位球，这些步骤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，并根据协调领域的影响揭示反应设计的生产性方向。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.