Modulation of Borylnitrene Reactivity in CH insertion and CC cycloaddition reactions by intramolecular dative Interactions

通过分子内配位相互作用调节硼基氮烯在 CH 插入和 CC 环加成反应中的反应性

• 批准号: 460087109
• 负责人: Professor Dr. Holger Bettinger
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/460087109?language=en
• 关键词: Modulation; Borylnitrene; Reactivity; CH; insertion

Nitrenes are reactive intermediates in organic synthesis. Borylnitrenes are boron derivatives that are particularly strong electrophilic species in their electronic singlet state. They react unselectively with CH bonds and can even activate the quite inert methane molecule. In this research project heterocyclic borylnitrenes of variable ring size (five to eight membered rings) and with variable hetero element (E = NR, O, S) are to be investigated. The variation of the conformational flexibility with ring size and the donor strength of E modulates the electronic structure and the reactivity of the borylnitrenes through the extend of the strength of the intramolecular E -> N dative interaction. The analysis of the structure – reactivity relationship of the borylnitrenes depending on ring size and donor element in CH insertions and [2+1] cycloadditions as typical representative nitrene reactions is the focus of this research project. Using the method of matrix isolation and classical solution phase product analyses the chemo-, regio-, diastereo- and enantioselectivity of borylnitrene chemistry are to be determined. It is expected that the research project provides fundamental insight into the reactivity of borylnitrenes and that it will be ultimately possible to tune reactivity employing intramolecular dative interactions.

氮烯是有机合成中的反应性中间体。硼基氮烯是硼衍生物，在电子单线态下是特别强的亲电子物质。它们与CH键无选择性地发生反应，甚至可以激活相当惰性的甲烷分子。在该研究项目中，将研究可变环尺寸（五至八元环）和可变杂元素（E = NR、O、S）的杂环硼基氮烯。构象灵活性随环尺寸和E的供体强度的变化通过扩展分子内E->N配位相互作用的强度来调节硼基氮烯的电子结构和反应性。本研究项目的重点是分析硼基氮烯的结构-反应性关系，具体取决于 CH 插入和 [2+1] 环加成反应中的环大小和供体元素。使用基质分离和经典溶液相产物分析的方法，可以确定硼基氮烯化学的化学选择性、区域选择性、非对映选择性和对映选择性。预计该研究项目将提供对硼基氮烯反应性的基本见解，并且最终将有可能利用分子内配位相互作用来调整反应性。