CAS: Computational and Experimental Mechanistic Approach to Understand and Develop Asymmetric Fe-Catalyzed Cross-Couplings with C(sp3) Fragments

CAS：理解和开发 C(sp3) 片段不对称 Fe 催化交叉偶联的计算和实验机制方法

• 批准号: 2246853
• 负责人: Osvaldo Gutierrez
• 金额: $ 57.5万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-04-01 至 2026-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246853&HistoricalAwards=false
• 关键词: CAS; Computational; Experimental; Mechanistic; Approach

With the support of the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) and the Chemical Catalysis (CAT) programs, Osvaldo Gutierrez of the Department of Chemistry at Texas A&M University will use a mechanistic-driven, multi-technique approach to design and develop asymmetric multicomponent Fe-catalyzed cross-coupling reactions involving stabilized carbon-centered radicals. The long-term goal of this work is to develop iron-catalyzed multicomponent cross-couplings to the level of palladium and nickel-based systems in terms of synthetic applications and mechanistic understanding. The project lies at the interface of organic synthesis and computational chemistry and is well-suited to train the next generation of organic chemists at all levels. In parallel to this research activities, Dr. Gutierrez will continue to evolve initiatives aimed at increasing the number of underrepresented minorities in science, technology, engineering and mathematics (STEM) fields by integrating education, research, and outreach through partnerships with the Alliance for Diversity in Science and Engineering (ADSE), TED-style talks, and expansion of on-going collaborative research and educational programs with the community colleges.The development of inexpensive, sustainable, and selective catalysts that can directly convert simple chemical “building blocks” to high-value chiral compounds remains a grand challenge in chemical synthesis. In this vein, there has been surge in the development of new iron-catalyzed cross-coupling reactions due to iron’s higher abundance in the earth’s crust, lower cost, and less toxic properties in comparison to most transition metal counterparts. However, in contrast to nickel- and palladium-based systems, the use of iron complexes capable of controlling enantioselectivity in catalytic carbon-carbon bond formation remains extremely rare. In this project, the Gutierrez research group will use a mechanistic-driven, multi-technique approach to design and develop asymmetric multicomponent Fe-catalyzed cross-coupling reactions involving allyl-and alpha-heteroatom bearing radicals. Efforts will include continuing to perform both high-level quantum mechanical calculations and experiments to accelerate reaction and catalyst design. There are potentially significant long term scientific broader impacts related to sustainable chemistry, particularly through the development of earth abundant transition metal catalysis.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.

在化学结构、动力学和机理-B (CSDM-B) 和化学催化 (CAT) 项目的支持下，德克萨斯农工大学化学系的 Osvaldo Gutierrez 将使用机械驱动的多技术方法来设计和开发涉及稳定碳中心自由基的不对称多组分铁催化交叉偶联反应这项工作的长期目标是开发铁催化的交叉偶联反应。该合成项目位于有机化学和计算化学的交汇处，非常适合培训下一代有机化学家。在开展这项研究活动的同时，古铁雷斯博士将继续制定举措，通过整合教育、研究和推广，增加科学、技术、工程和数学 (STEM) 领域代表性不足的少数群体的数量。与科学与工程多样性联盟 (ADSE) 的合作伙伴关系、TED 式的演讲，以及扩大与社区大学正在进行的合作研究和教育项目。开发廉价、可持续和选择性的催化剂，可以直接转化简单的催化剂高价值手性化合物的化学“构件”仍然是化学合成中的一个巨大挑战。在这方面，由于地壳中铁的丰度较高，铁催化的交叉偶联反应的发展激增。成本，并且更少与大多数过渡金属分子相比，铁络合物具有毒性。然而，与镍基和钯基体系相比，在催化碳-碳键形成中能够控制对映选择性的铁配合物的使用仍然极为罕见。该小组将使用机械驱动的多技术方法来设计和开发涉及烯丙基和α杂原子基团的不对称多组分铁催化交叉偶联反应。努力将包括继续进行高级量子力学计算和实验，以加速反应和催化剂设计，特别是通过开发地球上丰富的过渡金属催化，可能会对可持续化学产生重大的长期科学影响。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。

项目成果

Regioselective Fluoroalkylarylation of Enamides Enabled by an Iron-Catalyzed Multicomponent Radical Cross-Coupling Strategy

铁催化多组分自由基交叉偶联策略实现烯酰胺的区域选择性氟烷基芳基化

• DOI: 10.1021/acs.orglett.3c03059
• 发表时间: 2023-09-29
• 期刊: Organic Letters
• 影响因子: 5.2
• 作者: Ángel Rentería;Macayla Guerrero;Mireya Ramirez;O. Gutierrez
• 通讯作者: O. Gutierrez

Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

扩大烯醇甲硅烷基醚的化学空间：铁催化实现催化二碳官能化

• DOI: 10.1039/d3sc04549h
• 发表时间: 2023-11-22
• 期刊: Chemical Science
• 影响因子: 8.4
• 作者: Sar, Dinabandhu;Yin, Shuai;Grygus, Jacob;Renteria-Gomez, Angel;Garcia, Melanie;Gutierrez, Osvaldo
• 通讯作者: Gutierrez, Osvaldo