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

在化学结构、动力学和机理B(CSDM-B)和化学催化(CAT)计划的支持下，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的碳心自由基的不对称多组份Fe催化的交叉偶联反应。这项工作的长期目标是开发铁催化的多组分交叉偶联，在合成应用和机理理解方面达到钯和镍基体系的水平。该项目位于有机合成和计算化学的交界处，非常适合培养各级下一代有机化学家。在这些研究活动的同时，Gutierrez博士将继续推动旨在通过与科学与工程多样性联盟(ADSE)的合作伙伴关系、TED式讲座以及与社区大学正在进行的合作研究和教育计划的扩展来整合教育、研究和推广，从而增加科学、技术、工程和数学(STEM)领域中未被充分代表的少数族裔的数量的计划。开发廉价、可持续和选择性的催化剂，可以直接将简单的化学“积木”转化为高价值的手性化合物，仍然是化学合成中的一个巨大挑战。在这方面，由于铁在地壳中的丰度更高，成本更低，与大多数过渡金属相比较，毒性更小，因此新的铁催化的交叉偶联反应的开发激增。然而，与基于镍和钯的体系相比，能够在催化碳-碳键形成中控制对映体选择性的铁配合物的使用仍然非常罕见。在这个项目中，Gutierrez研究小组将使用机械驱动的多技术方法来设计和开发不对称的多组份Fe催化的交叉偶联反应，该反应涉及含烯丙基和α-杂原子的自由基。这些努力将包括继续进行高水平的量子力学计算和实验，以加速反应和催化剂设计。与可持续化学有关的潜在重大、长期和更广泛的科学影响，特别是通过开发地球上丰富的过渡金属催化剂。这一奖项反映了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 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.