Harnessing the Reactivity of Acceptor-Acceptor Diazo-Derived Metal Carbenes

在化学系化学合成项目的支持下，乔治亚理工学院的Stefan France正在研究一类重要的合成构件——受体-受体碳烯的性质，以确定如何调整它们的反应性，以实现可预测和可控的新键连接，用于合成增值化合物。虽然其他类型的碳烯具有更大的电子密度和稳定性，已经用各种催化剂进行了仔细的研究，以支持许多优雅的合成，但受体-受体碳烯却落后了。弗朗斯博士和他的研究小组正在使用实验和计算相结合的方法，通过汇编基础数据来了解如何控制和预测合成过程中受体-受体碳烯的反应性，从而解决这一限制。不同的催化剂也正在被研究，以从相同的碳基中获得不同的反应模式。这些研究通过研究合成化学这一领域的一个长期存在的问题，有助于改进精细化学品和药品的合成和制备。同时，这些活动通过与Seyhan Salman博士的计算合作，为佐治亚理工学院和克拉克亚特兰大大学（HBCU）的研究生和本科生提供跨学科培训。弗朗斯博士还参与了一个帮助研究生专业发展的项目，并致力于通过参与各种校园活动来解决多样性问题，以改善招聘和雇佣，以及学生保留率。由于缺乏对其反应性和稳定性的认识，受体-受体金属碳烯在分子间碳氢功能化化学中的应用不足。乔治亚理工学院的Stefan France和他的研究小组正在结合实验方法，并与克拉克亚特兰大大学的Seyhan Salman合作进行协作计算，以了解，参数化和预测受体-受体碳C(sp3)- h插入的底物和催化剂控制。此外，弗朗斯博士和他的研究小组正在探索新的受体-受体碳烯的不同反应模式。该项目将作为进入新化学领域的跳板，并开发使能技术，以改善获得理想目标分子的途径。这些活动还将为研究生和本科生提供与催化有机金属合成相关的计算和实验有机化学之间相互作用的培训。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。

With the support of the Chemical Synthesis Program in the Division of Chemistry, Stefan France of Georgia Tech is studying the properties of an important class of synthetic building blocks called acceptor-acceptor carbenes to determine how to tune their reactivity to achieve predictable and controllable new bond connections for the synthesis of value-added compounds. While other types of carbenes with greater electron-density and stability have been carefully studied with a variety of catalysts to support many elegant syntheses, acceptor-acceptor carbenes have lagged behind. Dr. France and his research team are using a combined experimental and computational approach to address this limitation by compiling fundamental data to understand how to control and predict the reactivity of acceptor-acceptor carbenes in synthetic processes. Different catalysts are also being investigated to achieve different reactivity patterns from the same carbene building blocks. These studies are helping to improve the synthesis and preparation of fine chemicals and pharmaceuticals by examining a long-standing problem in this area of synthetic chemistry. Simultaneously, these activities are providing interdisciplinary training for a diverse group of graduate and undergraduate students at Georgia Tech and Clark Atlanta University (an HBCU) through a computational collaboration with Dr. Seyhan Salman. Dr. France is also participating in a program to assist graduate students with professional development and is committed to addressing diversity issues through participation in a variety of campus initiatives to improve recruiting and hiring, as well as student retention.Acceptor-acceptor metal carbenes have been underutilized in intermolecular C-H functionalization chemistry due to a lack of understanding of their reactivity and stability properties. Stefan France and his research group at Georgia Tech are combining experimental approaches, and collaborative computational efforts in collaboration with Seyhan Salman at Clark Atlanta University, to understand, parametrize, and predict substrate- and catalyst-control for acceptor-acceptor carbene C(sp3)-H insertion. In addition, Dr. France and his research team are exploring new divergent reactivity patterns of acceptor-acceptor carbenes. This project will serve as a launching pad into new chemical space and for developing enabling technologies to improve access to desirable target molecules. These activities also will provide training to both graduate and undergraduate students on the interplay between computational and experimental organic chemistry of relevance to catalytic organometallic synthesis.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.