Enantioselective Functionalizations of alpha-, beta-Unsaturated Carboxylic Acids using Chiral Boronic Acids

烯烃的对映选择功能化在现代有机合成中起着十分重要的作用。到目前为止，已经报道了各种各样的不对称烯烃功能化，每周都有新的出版物出现在这个非常活跃的研究领域。然而，α，β-不饱和羧酸在烯烃转化中的使用仍然是相当未公开的，只有选定的反应，如氢化或环加成，是已知的。本文提出，手性硼酸的使用可能为α，β-不饱和羧酸的对映选择性功能化铺平道路。羧酸与硼酸应形成硼酸中间体，它可能容易发生几种转化，这将允许不对称制备范围广泛的功能化羧酸。该项目将缩小目前烯烃功能化状态的差距，并导致手性羧酸制备方法的发展，手性羧酸存在于大量药物和天然产品中。

The enantioselective functionalization of olefins plays a highly important role in modern organic synthesis. So far, a wide variety of asymmetric alkene functionalizations have been reported, with new publications appearing weekly on this very active research field. However, the use of α,β-unsaturated carboxylic acids in alkene transformations remains rather undisclosed and only selected reactions, such as hydrogenations or cycloadditions, are known.Herein it is proposed, that the use of a chiral boronic acid may pave the way for the enantioselective functionalization of α,β-unsaturated carboxylic acids. The carboxylic acid together with the boronic acid should form a boronate intermediate, which may be susceptible towards several transformations, which would allow the asymmetric preparation of a wide range of functionalized carboxylic acids. The project will close the gap in the current state of olefin functionalization and lead to the development of methodologies towards the preparation of chiral carboxylic acids, which are present in a large number of pharmaceuticals and natural products.