Reductive cross-coupling reactions of unsaturated compounds

化学部化学合成计划支持华盛顿大学化学系Gojko Lalic教授和他的团队的项目。拉里奇教授正在为有机合成开发一种新型的反应。这项研究的目标是提供一种更有效的替代传统方法，通过两个或更多的分子片段耦合(称为交叉偶联反应)来制造分子。与一步一步地构建分子相比，交叉偶联反应提高了合成工作的效率。交叉偶联反应通常用于精细化学品和药物的制备，因此与先进制造有关。这种新型的交叉偶联反应可以使用容易获得的化合物作为起始原料。与现有的最先进技术相比，新的反应提供了经济和环境优势。拉里奇博士和他的团队已经与推广科学技术的小学和高中建立了一个外展项目。一系列广泛的活动，包括定期参加当地高中的科学课程，旨在接触到科学方面代表性较低的学生，并促进科学、技术、工程和数学学科的职业生涯。在这个项目中，正在开发两种类型的不饱和化合物的还原交叉偶联反应。炔烃的合成选择性氢官能化被用于实现炔烃的氢芳基化、氢烯基化和氢烷基化。所有这三个转化都涉及到炔烃的氢铜化，然后是钯催化的烯基铜中间体的官能化。铜和钯催化剂协同作用的关键是两个不相容的组分的相分离；一个来自铜催化剂的催化循环，另一个来自钯催化剂的催化循环。相分离防止了一系列副反应，否则这些副反应将主导反应的结果。这一策略是通用的，可以用于开发其他需要两个不相容的催化循环协同催化的过程。LaLIC基团还在开发末端炔烃的反选择性氢化功能化方法。这些转化是基于最初的交叉偶联，然后是炔烃中间体的选择性半还原。该项目工作的另一个重要方面是Lalic教授和他的团队继续致力于在更广泛的社区中促进科学。这些努力的一个主要焦点是与当地项目和机构的合作，这些项目和机构专门支持未被充分代表的少数族裔学生和妇女参与STEM领域。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。

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Gojko Lalic and his group at the Department of Chemistry, University of Washington. Professor Lalic is developing a new type of reactions for organic synthesis. The goal of this research is to provide a more efficient alternative to traditional methods for making molecules by the coupling of two or more molecular fragments (reactions referred to as cross-coupling reactions). Cross-coupling reactions improve the efficiency of synthetic efforts relative to building molecules one step at a time. Cross-coupling reactions are commonly used in the preparation of fine chemicals and pharmaceuticals and thus, are relevant to advanced manufacturing. The new type of cross-coupling reactions enables the use of readily available compounds as starting materials. The new reaction provides economic and environmental advantages over the existing state-of-the-art. Dr. Lalic and his group have established an outreach program with elementary and high school schools that promote science and technology. A wide range of activities, including regular participation in science classes at local high schools, are designed to reach students underrepresented in science and promote careers in science, technology, engineering and mathematics disciplines.In this project, two types of reductive cross-coupling reactions of unsaturated compounds are being developed. Syn-selective hydrofunctionalization of alkynes are being used to enable the hydroarylation, hydroalkenylation, and hydroalkylation of alkynes. All three transformations involve hydrocupration of alkynes followed by palladium-catalyzed functionalization of the alkenyl copper intermediate. The key for the cooperative action of copper and palladium catalysts is a phase-separation of two incompatible components; one from a catalytic cycle of a copper catalyst and one from the catalytic cycle of a palladium catalyst. The phase separation prevents a series of side reactions that otherwise dominate the outcome of the reaction. This strategy is general and can be used to develop other processes that require cooperative catalysis of two incompatible catalytic cycles. The Lalic group is also developing methods for anti-selective hydrofunctionalization of terminal alkynes. These transformations are based on an initial cross coupling followed by the selective semireduction of the alkyne intermediate. Another important aspect of the work this project is the continued commitment of Professor Lalic and his group to promoting science in a broader community. A major focus of these efforts is a collaboration with local programs and institutions that specialize in supporting participation of underrepresented minority students and women in STEM fields.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.