GOALI: Development of General Methods to Access Functional Arylalkoxysilanes

在美国国家科学基金化学学部化学合成项目的支持下，中佛罗里达大学化学系教授Kangsang Lee开发了功能性芳基烷氧基硅烷的一般制备方法。有机硅是一种应用非常广泛的材料，在瓶子、化妆品、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都有应用。一组被称为烷氧基硅烷的化合物是制造有机硅材料中最常见的组成部分。然而，由于难以制备它们的细微变化，它们的效用受到限制。然而，有另一组潜在的有机硅构建块称为芳基烷氧基硅烷，它有可能克服烷氧基硅烷的局限性。在使用这类构建块时面临的一个主要问题是，有效地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芳烷烷氧基硅烷。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。这种合作和使用陶氏化学的设施，使李教授实验室取得的进步能够有效地评估它们在有机硅工业生产中的潜力。此外，它还为参与该项目的学生提供了示范性的教育经验。该项目将开发一些涉及芳烃和杂芳烃的催化C-H硅基化反应。目前，碳-氢硅基化反应仅限于反应性氢硅烷，如三烷基硅烷和硅氧氢硅烷，其结果是芳基硅烷不能直接用于硅氧烷聚合物的合成。有机硅合成中更理想的构建块是含烷氧基的芳基硅烷。然而，由于缺乏有效的合成方法，这些方法中只有少数是可用的。为了解决这一问题，本项目正在开发一种高效的铑催化的C-H硅基化反应在未活化的（杂）芳烃和单、二或三烷氧氢硅烷之间。该工艺旨在为各种芳烷氧基硅烷提供一种通用的方法。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。工业合作伙伴将为高通量筛选提供专业知识和设备，以确定潜在的催化剂，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，新的芳烷氧基硅烷将被评估为聚合物材料的前体。这方面的项目将包括实习，这将为参与的学生提供丰富的行业经验。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。

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.