光重排合成間位取代苯及其生物電子等排體

Abstract

光重排反應是一種獨特的有機化學反應，其中涉及利用光照來建構複雜的有機化合物分子結構。這些反應通常需要暴露在紫外線或可見光下，這會使分子中的電子從基態激發到激發態能階。此能階的變化導致共價鍵的斷裂和形成，最終形成與起始物截然不同的新分子。在這篇論文中，將描述兩種不同類型的光重排。在第一項研究中，雙環[3.1.0]己烷成功在室溫下透過光照而進行了重排，產生了難以通過傳統親電性芳香族取代反應獲得的對位取代酚。在第二項研究中，一種三環酮[3.3.0.02,3]藉由氧-雙π-甲烷重排反應被成功製備出來，可以作為合成間位取代苯的生物電子等排體的關鍵中間體，同時我們將描述對三環中羰基官能基衍生化的嘗試。

Photorearrangement is a unique type of organic transformation that involves the use of light to reconfigure the molecular framework of organic compounds. These reactions typically require exposure to ultraviolet or visible light, which excites electrons in the molecules from their ground states to excited energy levels. This excitation leads to the breaking and formation of chemical bonds, resulting in a new molecule. In this thesis, two different types of photorearrangements will be described. In the first study, bicyclo[3.1.0]hex-3-en-2-ones have been successfully rearranged at room temperature through exposure to light, yielding meta-substituted phenols that are difficult to obtain through traditional synthetic methods. In the second study, a tricyclic ketone, which could serve as a key intermediate to access meta-substituted benzene bioisosteres, was prepared through an oxa-di-π-methane (ODPM) rearrangement. Our attempts to functionalize the ketone moiety will be described.