GOALI: Development of General Methods to Access Functional Arylalkoxysilanes

目标：开发获取功能性芳基烷氧基硅烷的通用方法

• 批准号: 2246567
• 负责人: Kangsang Lee
• 金额: $ 49.93万
• 依托单位: The University of Central Florida Board of Trustees
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246567&HistoricalAwards=false
• 关键词: GOALI; Development; General; Methods; Access

With the support of the Chemical Synthesis program of the Division of Chemistry of the National Science Foundation, Professor Kangsang Lee, Department of Chemistry at the University of Central Florida, is supported to develop general methods for the preparation of functional arylalkoxysilanes. Silicones are very widely used materials and are found in common consumer products such as bottles, cosmetic products, and cookware as well as in high-tech automotive, electronic, aeronautic and biomedical applications. A group of compounds called alkoxysilanes are the most common building blocks in the manufacture of silicone materials. However, their utility is limited due to difficulties in preparing subtle variations of them. However, there is another group of potential silicone building blocks called arylalkoxysilanes that potentially can overcome the limitations of the alkoxysilanes. A major problem faced in employing this class of building blocks is that methods the efficiently prepare them are not known. Thus, this project aims at developing a direct and atom-economical pathway to synthesize a wide variety of arylalkoxysilanes. The project involves a close collaboration between Professor Lee’s group and scientists at Dow Chemical Company. This collaboration and the access to facilities at Dow permits the advances made in Professor Lee’s laboratories to be efficiently evaluated for their potential in the industrial manufacture of silicones. Additionally, it provides exemplary educational experiences to the students who will be engaged in the project. This project will develop a number of catalytic C–H silylation reactions involving arenes and heteroarenes. Carbon-hydrogen silylation reactions are currently limited to reactive hydrosilanes such as trialkylsilanes and siloxyhydrosilanes and result in arylsilanes that cannot be directly utilized in siloxane polymer synthesis. More desirable building blocks in silicone syntheses are alkoxy-containing arylsilanes. However, only a few of these are available due to the lack of efficient synthetic methodologies. To address this problem this project an efficient rhodium catalyzed C–H silylation between unactivated (hetero)arenes and mono-, di- or trialkoxyhydrosilanes is being developed. The process is designed to provide a general methodology to a variety of arylalkoxysilanes. The project involves close collaboration between Professor Lee’s group and scientists at Dow Chemical Company. The industrial partner will provide expertise and the facilities for in high-throughput screening to identify potential catalysts and will apply these results to uncover structure-property relationships to guide further synthetic efforts. Additionally, the new arylalkoxysilanes will be evaluated as precursors to polymeric materials. This aspect of the project will involve internships, which will provide rich industrial experiences to the students involved.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.

在美国国家科学基金会化学部化学合成项目的支持下，中央佛罗里达大学化学系的李康桑教授得到了支持，以开发制备官能化芳基烷氧基硅烷的一般方法。有机硅是一种用途非常广泛的材料，广泛应用于瓶子、化妆品和炊具等普通消费品以及高科技汽车、电子、航空和生物医学应用中。一组称为烷氧基硅烷的化合物是有机硅材料制造中最常见的结构单元。然而，由于难以制备它们的细微变化，它们的实用性受到限制。然而，存在另一组称为芳基烷氧基硅烷的潜在有机硅结构单元，其潜在地可以克服烷氧基硅烷的限制。采用这类结构单元所面临的主要问题是，有效制备它们的方法是未知的。因此，本项目旨在开发一种直接和原子经济的途径来合成各种各样的芳基烷氧基硅烷。该项目涉及李教授的小组和陶氏化学公司的科学家之间的密切合作。这种合作以及陶氏化学设施的使用使得李教授的实验室所取得的进展能够有效地评估其在有机硅工业生产中的潜力。此外，它还为将参与该项目的学生提供了示范性的教育经验。本计画将发展一系列芳烃及杂芳烃的C-H硅烷化催化反应。碳-氢甲硅烷基化反应目前限于反应性氢硅烷，例如三烷基硅烷和二烷基氢硅烷，并且产生不能直接用于硅氧烷聚合物合成的芳基硅烷。有机硅合成中更理想的结构单元是含烷氧基的芳基硅烷。然而，由于缺乏有效的合成方法，只有少数这些是可用的。为了解决这个问题，该项目正在开发未活化的（杂）芳烃与单-、二-或三烷氧基氢硅烷之间的有效铑催化的C-H甲硅烷基化。该方法旨在为各种芳基烷氧基硅烷提供通用方法。该项目涉及李教授的小组和陶氏化学公司的科学家之间的密切合作。工业合作伙伴将提供高通量筛选的专业知识和设施，以识别潜在的催化剂，并将这些结果应用于揭示结构-性质关系，以指导进一步的合成工作。此外，新的芳基烷氧基硅烷将作为聚合物材料的前体进行评估。该项目的这一方面将涉及实习，这将为参与的学生提供丰富的工业经验。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。