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

利用受体-受体重氮衍生金属卡宾的反应性

• 批准号: 2102472
• 负责人: Stefan France
• 金额: $ 47.5万
• 依托单位: Georgia Tech Research Corporation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102472&HistoricalAwards=false
• 关键词: Harnessing; Reactivity; Acceptor; Diazo; Derived

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.

在化学部化学合成计划的支持下，佐治亚理工学院的斯特凡·弗兰斯正在研究一类重要的合成构件-受体-受体卡宾的性质，以确定如何调节它们的反应性，以实现可预测和可控制的新键连接，用于合成增值化合物。虽然其他类型的卡宾具有更高的电子密度和稳定性，已经用各种催化剂仔细研究了许多优雅的合成，但受体-受体卡宾却落后了。法兰西博士和他的研究团队正在使用一种实验和计算相结合的方法来解决这一局限性，方法是汇编基础数据，以了解如何在合成过程中控制和预测受体-受体卡宾的反应性。还在研究不同的催化剂，以从相同的卡宾构建块实现不同的反应模式。这些研究正在通过研究合成化学领域中的一个长期存在的问题，帮助改进精细化学品和药物的合成和制备。与此同时，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)的不同研究生和本科生提供跨学科培训。法国博士还参与了一项帮助研究生进行专业发展的计划，并致力于通过参与各种校园倡议来解决多样性问题，以改善招生和招聘以及学生保留率。由于缺乏对分子间C-H官能化化学的反应性和稳定性的了解，接受者-接受者金属卡宾在分子间C-H官能化化学中一直没有得到充分利用。乔治亚理工学院的Stefan France和他的研究小组正在与克拉克亚特兰大大学的Seyhan Salman合作，将实验方法和协作计算工作结合起来，以了解、参数化和预测受体-受体卡宾C(SP3)-H插入的底物和催化剂控制。此外，弗兰奇博士和他的研究团队正在探索受体-受体卡宾的新的不同反应模式。该项目将作为进入新的化学空间的发射台，并用于开发使能技术，以改善获得理想的目标分子的机会。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有机化学和实验有机化学之间的相互作用的培训。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。

项目成果

Rh(II)‐catalyzed Intermolecular Benzylic C(sp 3 )−H Alkylation of Methyl‐substituted Arenes by N ‐Aryl‐α‐diazo‐β‐amidoesters

Rh(II)—催化 N—芳基—芳基—重氮—氨基酯对甲基—取代芳烃的分子间苯甲基 C(sp 3 )—H 烷基化

• DOI: 10.1002/cctc.202101977
• 发表时间: 2022
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: Yuan, Shaoren;McLaren, Eric J.;France, Stefan
• 通讯作者: France, Stefan