芳基高价碘参与的[3,3]-重排反应

芳烃重排反应是芳烃衍生化的重要手段，可提供用途广泛的多取代芳烃，因此长期以来都是合成化学的重要研究方向。近来，申请人在研究中意外发现，芳基亚砜与烷基腈的[3,3]-重排反应，由此提出“组装/脱质子”引发重排的策略。借助该策略，申请人进一步发展了几种非传统的芳基重排反应。其中，芳基高价碘的重排反应，因其给出的产物含有碘原子，有利于产物的进一步衍生化，而更具发展前景。然而，该类反应因高价碘中间体稳定性差，导致反应底物适用范围窄、反应模式单一的问题。在前期工作的基础上，申请人将通过本项目，进一步借助“组装/脱质子”的策略，探寻兼容性更好的反应体系，发展普通羰基化合物的重排反应以及相应的不对称重排过程，并将“组装”策略与Morita-Baylis-Hillman反应融合，发展“组装/加成”型重排反应，最终实现一系列非传统的芳烃重排过程，为多取代芳烃的合成提供新方法。

Aromatic rearrangement is an essential protocol for derivatizing arenes that can produce valuable and widely used poly-substituted arenes. Therefore, the rearrangement reaction has long been an important area of synthetic chemistry. Recently, the applicant serendipitously discovered the [3,3]-rearrangement of aryl sulfoxides with alkyl nitriles. This study led to the establishment of an “assembly/deprotonation” protocol that can be used for triggering the rearrangement process. With the newly developed protocol, the applicant developed several unconventional rearrangement reactions. Among them, [3,3]-rearrangement of aryl iodanes is more attractive since the process remains an iodide atom in products that is beneficial for further elaboration of the products. However, due to the instability of aryl iodine(III) intermediates, this type of reactions have long suffered from the limited substrate scope and the inflexible reaction pattern. On the basis of previous work, the applicant will apply the “assembly/deprotonation” protocol for exploring new reaction systems with higher compatibility to realize the rearrangement of common carbonyl compounds and corresponding asymmetric rearrangements. Furthermore, the “assembly/addition” rearrangement reaction will also be developed by merging the “assembly” protocol with the Morita-Baylis-Hillman reaction. In a word, the project aims to develop an array of unconventional aromatic rearrangement processes, eventually providing new approaches to valuable poly-substituted arenes.