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RUI: Accessing Asymmetric Carbon Atoms by Samarium(II)-Water Allylic Benzoate Reductions

RUI：通过钐(II)-水烯丙基苯甲酸酯还原获得不对称碳原子

基本信息

批准号：
1760918
负责人：
Gregory O'Neil
金额：
$ 25.65万
依托单位：
Western Washington University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-08-01 至 2024-01-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1760918&HistoricalAwards=false
关键词：
RUI Accessing Asymmetric Carbon Atoms

项目摘要

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Gregory O'Neil. Professor O'Neil is a faculty member in the Department of Chemistry at Western Washington University. He is developing new reactions that allow access to one mirror image of a carbon atom over another. Many important molecules (e.g. medicinal natural products) and materials exist as a single mirror image with their activity directly related to that specific mirror image. Hence, methods to control which mirror image of a carbon atom is formed are essential for the construction of molecules that have the correct biological activity. Accordingly, Professor O-Neil and his group are harnessing the unique chemistry of samarium(II)-water complexes to achieve this goal. The reactions were chosen because samarium(II) is readily available, and the ability to perform the reactions in water obviates special handling or equipment requirements. Thus, the chemistry is readily adoptable by others, well suited for research at a primarily undergraduate institution, and compatible with incorporation into an Introductory Organic Laboratory course. In addition, student participants are learning a variety of research methods including organic synthesis and advanced analytical techniques. They become integrated into the scientific community through attendance at professional meetings and dissemination of results using both standard (e.g. scientific papers and posters) and less traditional outlets (e.g. podcasts, videos, magazine articles). Professor O'Neil's group is well positioned to provide this experience for students underrepresented in science.The ability to generate stereogenic carbons with absolute stereocontrol is a requirement for many compelling synthetic targets. The goal of this project is to investigate the use of SmI2(H2O)n for allylic benzoate reductions. The combination leads a highly versatile and accessible method for the synthesis of asymmetric carbon atoms. The reactions are potentially powerful because they provide a solution to an existing challenge that does not require the use of specialized reagents, is easy to execute, and has a broad substrate scope and functional group tolerance. The methods are capable of generating asymmetric carbon atoms that can be difficult to construct with other methods, they consistently and predictably lead to stereoselectivities that are controllable by starting substrate structure and independent of the groups attached to the newly formed stereogenic carbon, they are straightforward to conduct using readily available reagents/substrates and with water (thereby allowing for functional groups (e.g. -OH) often not tolerated), and they are controlled by a stereo-differentiating group that can either be incorporated into the final target or be recycled as a chiral auxiliary. Broader impacts and educational components of the project include the development and implementation of a 4-day undergraduate laboratory experiment that teaches concepts related to stereochemistry and the methods needed for isomer ratio determination. This work will also create a repository with optical activity data for various chiral aldehydes available for use by other groups.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.

化学系的化学合成计划支持格雷戈里·奥尼尔教授的项目。奥尼尔教授是西华盛顿大学化学系的教员。他正在开发新的反应，允许访问一个碳原子的镜像在另一个。许多重要的分子（例如药用天然产物）和材料作为单一镜像存在，其活性与该特定镜像直接相关。因此，控制碳原子形成镜像的方法对于构建具有正确生物活性的分子至关重要。因此，O-Neil教授和他的团队正在利用钐（II）-水络合物的独特化学性质来实现这一目标。选择这些反应是因为钐（II）容易获得，并且在水中进行反应的能力消除了特殊的处理或设备要求。因此，该化学很容易被其他人采用，非常适合主要本科院校的研究，并且适合纳入有机实验室入门课程。此外，学生参与者正在学习各种研究方法，包括有机合成和先进的分析技术。他们通过参加专业会议和利用标准（如科学论文和海报）和非传统渠道（如播客、视频、杂志文章）传播成果，融入科学界。O 'Neil教授的团队很好地为科学领域代表性不足的学生提供了这种经验。在绝对立体控制的情况下生成立体碳的能力是许多引人注目的合成目标的要求。本项目的目标是研究使用SmI 2（H2O）n的烯丙基苯甲酸酯的减少。该组合为合成不对称碳原子提供了一种高度通用且易于获得的方法。这些反应可能是强大的，因为它们提供了一种解决现有挑战的方法，不需要使用专门的试剂，易于执行，并且具有广泛的底物范围和官能团耐受性。所述方法能够产生难以用其它方法构建的不对称碳原子，它们一致地且可预测地导致立体选择性，所述立体选择性可通过起始底物结构控制并且不依赖于连接到新形成的立体碳上的基团，它们直接使用容易获得的试剂/底物和水进行（从而允许通常不耐受的官能团（例如-OH）），并且它们由立体分化基团控制，所述立体分化基团可以并入最终靶标中或作为手性助剂再循环。该项目更广泛的影响和教育部分包括制定和实施一个为期4天的本科生实验室实验，教授与立体化学有关的概念和异构体比例测定所需的方法。这项工作还将创建一个储存库，其中包含各种手性醛的旋光活性数据，可供其他团体使用。该奖项反映了NSF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。