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.

化学部的化学综合计划由华盛顿大学化学系的Gojko Lalic教授及其小组支持该项目。 Lalic教授正在开发一种新型的有机合成反应。这项研究的目的是通过耦合两个或多个分子片段（反应称为交叉偶联反应），为传统方法提供更有效的替代方法。交叉偶联反应一次相对于建立分子一次步骤提高了合成努力的效率。 交叉偶联反应通常用于制备精细化学物质和药物，因此与晚期制造有关。新型的交叉耦合反应可以将随时可用的化合物用作起始材料。与现有的最新反应相比，新反应提供了经济和环境的优势。 Lalic博士和他的小组已经通过促进科学和技术的小学和高中学校建立了一项外展计划。各种各样的活动，包括定期参加当地高中的科学课程，旨在吸引科学领域不足的学生，并促进科学，技术，工程和数学学科的职业。炔烃的合成 - 选择性水功能化被用来实现炔烃的氢碳化，氢烯基化和氢烷基化。这三个转化均涉及炔烃的氢化，然后进行钯催化的烷基铜中间体功能化。铜和钯催化剂合作作用的关键是两个不兼容的成分的相分开。一种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。相位分离阻止了一系列副反应，这些反应原本主导了反应的结果。该策略是一般的，可用于开发其他需要对两个不相容的催化周期进行合作催化的过程。 LALIC组还正在开发用于末端炔烃抗选择性水功能化的方法。这些转换基于初始交叉耦合，然后是炔烃中间体的选择性半元素。该项目的另一个重要方面是Lalic教授及其小组在更广泛的社区中促进科学的持续承诺。这些努力的重点是与本地计划和机构进行合作，专门支持代表性不足的少数民族学生和女性在STEM领域的参与。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的审查标准通过评估来进行评估的。