Metal Catalyzed Methods for the Preparation of Organosilanes and Related Molecules

金属催化制备有机硅烷及相关分子的方法

• 批准号: 2102077
• 负责人: Donald Watson
• 金额: $ 50万
• 依托单位: University of Delaware
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102077&HistoricalAwards=false
• 关键词: Metal; Catalyzed; Methods; Preparation; Organosilanes

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Donald A. Watson of the University of Delaware is studying the new catalytic methods to prepare organic molecules that contain silicon atoms. Such molecules, commonly called organosilanes, are important building blocks for the complex organic chemical compounds that are used as pharmaceuticals, as agrochemicals, and for the study of biology. This research aims to develop new reactions that allow for these important silicon containing compounds to be prepared in new, straightforward ways using inexpensive starting materials and catalytic amounts of reaction promoters. Not only will this research expand access to organosilanes, but it will also increase fundamental understanding of the reactions silicon containing molecules and their interactions with transition metal catalysts. The program will also train undergraduate student, graduate student and post-doctoral researchers, and will build outreach programs to both early childhood education and undergraduate-only higher educations institutions that lack advanced research technology. In so doing, the research program will seek to train the next generation of chemical scientist who will tackle the challenges of tomorrow. The focus of the research program is the development of new cross-coupling reactions of electrophilic silanes. Using transition metal catalysts, Dr. Donald Watson and his students seek to develop new methods for C-Si bond construction to prepare a variety of both saturated and unsaturated organosilanes via cross-coupling with simple organic nucleophiles. To achieve this result, the Watson group has designed a new type of silyl-Heck reaction with analogy to the robust and highly studied parent Heck reaction of alkenes. This newer silyl variant of the Heck coupling is expected to permit access to otherwise challenging vinylic and allylic silane targets. The Watson team then seeks to develop related multi-component transformations to access even more complex and highly substituted alkylsilanes. In parallel to the development of these new synthetic methods, Dr. Watson and his students will seek to elucidate the underlying mechanism(s) of the transformations under study. Therefore, this project will provide exposure to synthetic, mechanistic and physical organic chemistry for the student and postdoctoral co-workers on the team, and in this way prepare them well for future careers in industry or academia.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.

在化学系化学合成（SYN）项目的支持下，唐纳德A。特拉华州大学的沃森正在研究新的催化方法来制备含有硅原子的有机分子。这些分子通常称为有机硅烷，是用作药物、农用化学品和生物学研究的复杂有机化合物的重要组成部分。这项研究旨在开发新的反应，允许这些重要的含硅化合物以新的，直接的方式使用廉价的起始材料和催化量的反应促进剂制备。这项研究不仅将扩大有机硅烷的使用范围，而且还将增加对含硅分子反应及其与过渡金属催化剂相互作用的基本理解。该计划还将培训本科生，研究生和博士后研究人员，并将为缺乏先进研究技术的幼儿教育和本科生高等教育机构建立推广计划。通过这样做，该研究计划将寻求培养下一代化学科学家，他们将应对明天的挑战。该研究计划的重点是开发亲电硅烷的新交叉偶联反应。利用过渡金属催化剂，Donald沃森博士和他的学生寻求开发C-Si键构建的新方法，通过与简单有机亲核试剂的交叉偶联制备各种饱和和不饱和有机硅烷。为了实现这一结果，沃森小组设计了一种新型的甲硅烷基-赫克反应，类似于烯烃的稳健和高度研究的母体赫克反应。 这种较新的甲硅烷基变体的赫克耦合，预计将允许访问，否则具有挑战性的乙烯基和烯丙基硅烷的目标。 然后，沃森团队寻求开发相关的多组分转化，以获得更复杂和高度取代的烷基硅烷。在开发这些新的合成方法的同时，沃森博士和他的学生将寻求阐明所研究的转化的潜在机制。 因此，该项目将为团队中的学生和博士后同事提供合成，机械和物理有机化学的接触，并以这种方式为他们未来在工业或学术界的职业生涯做好准备。该奖项反映了NSF的法定使命，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

Development of a General Method for the Hiyama-Denmark Cross-Coupling of Tetrasubstituted Vinyl Silanes.

• DOI: 10.1021/acscatal.2c03981
• 发表时间: 2022-10-21
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Pawley, Sarah B.;Conner, Allyssa M.;Omer, Humair M.;Watson, Donald A.
• 通讯作者: Watson, Donald A.

Selected Ion Monitoring Using Low-Cost Mass Spectrum Detectors Provides a Rapid, General, and Accurate Method for Enantiomeric Excess Determination in High-Throughput Experimentation.

• DOI: 10.1021/acscatal.2c01628
• 发表时间: 2022-06-03
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Korch, Katerina M.;Hayes, Jacob C.;Kim, Raphael S.;Sampson, Jessica;Kelly, Austin T.;Watson, Donald A.
• 通讯作者: Watson, Donald A.