RUI: Contributions of Heavy-Atom Quantum Tunneling to Reactivity in Organic Chemistry

美国国家科学基金会化学部的化学结构，动力学和机制-B计划正在支持纽约市立大学巴鲁克学院Edyta Greer教授的研究。Greer教授的研究重点是有机反应中的热激活重原子隧穿。确定热激活重原子隧穿的贡献水平对于理解这些反应中的机理细节至关重要。 机械细节可以导致更有效的反应的发展，这在化学和制药工业中是重要的。 这项研究也与量子信息科学有关，可能有助于理解量子计算，通信和传感。 这项研究将与纽约市立大学巴鲁克学院的本科课程相结合。外联活动包括在当地小学举行教育讲座，通过演示和实验向年轻一代学生传达STEM的重要性。热激活的重原子隧穿是一个基本的过程，其中隧穿势垒可能有助于反应速率。其在有机反应中的流行程度仍然不确定，部分原因是其定量的挑战。这个项目寻求一种计算方法来评估热激活重原子隧穿。三类反应是有针对性的：羰基和烯烃的分子内复分解反应;硒氧化物的顺式消除反应;和螺旋烯的电环化。Greer教授的研究团队将在中、高能量屏障区域确定“甜蜜点”，为有机化学机理提供所需的见解。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

The Chemical Structure, Dynamics and Mechanisms-B Program of the Chemistry Division of NSF is supporting the research of Professor Edyta Greer at CUNY Baruch College. Professor Greer’s research focuses on thermally-activated heavy-atom tunneling in organic reactions. Determining the level of contributions of thermally-activated heavy-atom tunneling is critical to understand mechanistic details in these reactions. Mechanistic details can lead to the development of more efficient reactions, which are important in the chemical and pharmaceutical industrials. This research also has relevance to quantum information science and may be useful in helping to understand quantum computing, communication and sensing. The research will be integrated with undergraduate curriculum at CUNY Baruch College. Outreach activities include educational talks at local elementary schools using demonstrations and experiments to convey the importance of STEM to the youngest generations of students. Thermally-activated heavy-atom tunneling is a fundamental process in which tunneling through the barrier can potentially contribute to reaction rates. Its prevalence in organic reactions remains uncertain in part due to challenges with its quantitation. This project seeks a computational approach to assess thermally-activated heavy-atom tunneling. Three classes of reactions are targeted: intramolecular metathesis reactions of carbonyls and olefins; syn-elimination reactions of selenoxides; and electrocyclizations of helicenes. Professor Greer’s research team will identify “sweet spots” in mid and upper energy barrier regions to provide the needed insight to mechanistic organic chemistry.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.