Towards Absolute Asymmetric Synthesis

走向绝对不对称合成

• 批准号: 1665109
• 负责人: Tehshik Yoon
• 金额: $ 45万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2020-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665109&HistoricalAwards=false
• 关键词: Towards; Absolute; Asymmetric; Synthesis

This award from the Chemical Synthesis Program of the Chemistry Division goes to support research by Professor Tehshik Yoon of the University of Wisconsin-Madison's Chemistry Department. Professor Yoon is interested in the "chirality", or "handedness", of small organic molecules. Many important organic molecules, including drug molecules and biologically important molecules like amino acids and sugars can exist in either left- or right-handed forms, with only one form being biologically desirable. The undesirable form can be harmful, so almost all new drug-candidates or diagnostic probes must be of only one "handedness". Light can also be produced with either left- or right-handed circular polarizations. The long-term goal of this project is to use the handedness of circularly polarized light to dictate the handedness of a small organic molecule. This is accomplished by designing helically chiral catalysts that can first be selectively activated by circularly polarized light with only one handedness and then transferring that handedness to a chemical reaction and its resultant product. This project requires an interdisciplinary approach that combines synthetic organic chemistry, organometallic chemistry, photochemistry, and computational chemistry to achieve its objectives, and in that way it provides outstanding training for students. Professor Yoon is also a leader in efforts to increase the diversity of students who undertake careers in science, and the project includes broader impacts that continue these important efforts. The chiral photocatalysts studied in this project are octahedral iridium complexes whose ligands are arranged about the metal with well-defined helical chirality. This class of compounds constitutes an attractive starting point for these studies because they possess a robust and well-studied photochemistry, because they have been recently shown to be quite effective photosensitizers for a range of organic transformations, and because they can easily be synthesized in stereochemically pure form. The first phase of this project shows that the chirality of a single enantiomer of a helically chiral iridium photocatalyst can be transmitted to a newly formed organic photocycloadduct. The second phase seeks understanding of the structure-activity relationships necessary for effective enantioselective photocatalysis. The third and most ambitious phase attempts to identify orthogonal structural features that enable selective activation of a racemic mixture of chiral Ir photocatalysts with circularly polarized light. The broader impacts of this project train a diverse set of graduate, undergraduate, and postdoctoral researchers in cutting-edge synthetic organic chemistry relevant to the construction of potential new drugs, materials, and fine chemicals.

该奖项来自化学系化学合成项目，旨在支持威斯康星大学麦迪逊分校化学系Tehshik Yoon教授的研究。 尹教授对有机小分子的“手性”或“手性”感兴趣。许多重要的有机分子，包括药物分子和生物学上重要的分子，如氨基酸和糖，可以以左手或右手形式存在，只有一种形式是生物学上所需的。不受欢迎的形式可能是有害的，所以几乎所有的新候选药物或诊断探针必须只有一个“手性”。光也可以产生左旋或右旋圆偏振。这个项目的长期目标是利用圆偏振光的旋向性来决定有机小分子的旋向性。这是通过设计螺旋手性催化剂来实现的，该催化剂可以首先被仅具有一个手性的圆偏振光选择性地激活，然后将该手性转移到化学反应及其所得产物中。该项目需要一种跨学科的方法，将合成有机化学，有机金属化学，光化学和计算化学相结合，以实现其目标，并以这种方式为学生提供出色的培训。尹教授也是努力增加从事科学职业的学生多样性的领导者，该项目包括继续这些重要努力的更广泛的影响。本项目所研究的手性光催化剂是八面体铱配合物，其配体以螺旋手性排列在金属周围。 这类化合物构成了这些研究的一个有吸引力的起点，因为它们具有强大的和充分研究的光化学，因为它们最近已被证明是相当有效的光敏剂的有机转化范围，因为它们可以很容易地合成立体化学纯的形式。 该项目的第一阶段表明，螺旋手性铱光催化剂的单一对映体的手性可以传递到新形成的有机光环加合物。 第二阶段寻求有效的对映选择性异构化所必需的结构-活性关系的理解。 第三个也是最雄心勃勃的阶段试图确定正交的结构特征，使选择性激活手性Ir光催化剂的外消旋混合物与圆偏振光。该项目的更广泛的影响培养了一批不同的研究生，本科生和博士后研究人员，他们从事与潜在新药，材料和精细化学品的构建相关的尖端合成有机化学研究。