Reductive cross-coupling reactions of unsaturated compounds

不饱和化合物的还原交叉偶联反应

• 批准号: 1800356
• 负责人: Gojko Lalic
• 金额: $ 42万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-15 至 2021-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800356&HistoricalAwards=false
• 关键词: Reductive; cross; coupling; reactions; unsaturated

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.

化学部化学合成项目支持华盛顿大学化学系Gojko Lalic教授及其团队的项目。拉利克教授正在研究一种新型的有机合成反应。本研究的目标是提供一种更有效的替代传统方法，通过耦合两个或多个分子片段来制造分子（称为交叉耦合反应的反应）。相对于一步一步地构建分子，交叉偶联反应提高了合成效率。交叉偶联反应通常用于精细化学品和药品的制备，因此与先进制造业有关。这种新型的交叉偶联反应可以使用现成的化合物作为起始材料。与现有的最先进的反应相比，新的反应具有经济和环境优势。拉里克博士和他的团队已经在小学和中学建立了一个推广科学技术的项目。广泛的活动，包括定期参加当地高中的科学课程，旨在接触在科学领域代表性不足的学生，并促进科学、技术、工程和数学学科的职业发展。本项目主要研究了两种不饱和化合物的还原性交叉偶联反应。炔的同步选择性加氢功能化被用于实现炔的加氢芳基化、加氢烯基化和加氢烷基化。所有这三种转化都涉及炔的加氢化，然后是钯催化的烯基铜中间体的功能化。铜钯催化剂协同作用的关键是两种不相容组分的相分离；一个来自铜催化剂的催化循环，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，否则这些副反应会主导反应的结果。这种策略是通用的，可用于开发其他需要两个不相容的催化循环的协同催化的过程。拉利克小组也在开发末端炔的反选择性加氢功能化方法。这些转化是基于初始交叉耦合，然后选择性半还原炔烃中间体。这项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推广科学。这些努力的一个主要重点是与专门支持代表性不足的少数民族学生和妇女参与STEM领域的当地项目和机构合作。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。