From Molecular Iodine to Chiral Catalysts - Systematic Applications of Halogen-Bonding in Organocatalysis

从分子碘到手性催化剂 - 卤素键在有机催化中的系统应用

• 批准号: 388141366
• 负责人: Professor Dr. Martin Breugst
• 金额: --
• 依托单位: Institut für Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/388141366?language=en
• 关键词: Molecular; Iodine; Chiral; Catalysts; Systematic

The research will advance the field of halogen bonding and its systematic application in organic synthesis. Specifically, we will focus on the development of stereoselective halogen-bond-catalyzed reactions and the design of the required chiral catalysts. So far, halogen bonding has successfully been employed in different field of chemistry including organic catalysis, but stereoselective transformations caused by halogen bonds are scarce. To close this gap, we combine classical physical-organic and spectroscopic techniques and computational investigations with synthetic experiments. We will identify chiral additives that are capable of complexing molecular iodine, one of the simplest halogen-bond donors, to create a chiral environment that results in enantioselective transformations. Furthermore, we will construct a Lewis-acidity scale for different halogen-bond motifs that allows us to identify promising candidates for catalysis. Those catalysts will complement the currently employed proline- or prolinol-derived structures. We demonstrate the activity of these newly identified catalysts in important organocatalytic transformations.Therefore, our investigations offer on the one hand a new perspective on the field of organocatalysis by the introduction of new motifs. On the other hand, the physical-organic analysis will provide deep insights into crucial aspects of this unexplored noncovalent interaction.

该研究将对卤素键合反应及其在有机合成中的系统应用起到推动作用。具体地说，我们将专注于立体选择性卤键催化反应的发展和所需手性催化剂的设计。到目前为止，卤键已成功地应用于包括有机催化在内的各个化学领域，但由卤键引起的立体选择性转化还很少。为了缩小这一差距，我们将经典的物理-有机和光谱技术以及计算研究与合成实验相结合。我们将确定能够络合分子碘的手性添加剂，碘是最简单的卤键供体之一，以创造导致对映选择性转化的手性环境。此外，我们将为不同的卤键基序构建一个Lewis酸度标度，使我们能够确定有希望的催化候选者。这些催化剂将补充目前使用的脯氨酸或脯氨醇衍生结构。我们展示了这些新发现的催化剂在重要的有机催化转化中的活性。因此，我们的研究一方面通过引入新的基序为有机催化领域提供了一个新的视角。另一方面，物理-有机分析将为这种未被探索的非共价相互作用的关键方面提供深刻的见解。