有机催化不对称烯丙基烷基化反应合成非碳中心手性化合物

近年来，非碳中心手性如轴手性、磷中心手性、硫中心手性、硅中心手性等化合物引起了化学家们的高度关注，它们不仅可以作为手性催化剂或手性配体应用于不对称催化反应，其骨架还广泛存在于天然产物、药物以及生物活性分子中。正是由于这些化合物表现出的优良性质，使得非碳中心手性化合物的合成研究已然成为当前有机化学的热点领域。因此，发展有机催化的通用策略来实现非碳中心手性化合物在温和条件下的高效合成方法，就变得非常有意义，也是一个极具挑战的难题。本课题打破传统有机路易斯碱催化以MBH加成物为烯丙基化试剂的不对称烯丙基烷基化反应的局限，采用非前手性MBH加成物与杂原子亲核试剂开展反应，避免了成键时手性碳的形成，来实现非碳中心手性化合物的合成，并将所合成化合物应用于不对称催化反应中。

Recently, the applications of non-carbon-centered chiral compounds, such as axially chiral, phosphorus-centered chiral, sulfur-centered chiral and silicon-centered chiral compounds etc, have attracted chemists’ great attention. These non-carbon-centered chiral compounds not only used as chiral catalysts or ligands in asymmetric catalysis, but also widely existed in natural products, drugs and bioactive molecules. Because of the excellent properties of these compounds, the synthesis of non-carbon-centered chiral compounds has become a hot topic of organic chemistry. Therefore, the development of general strategies using organocatalysis to achieve efficient synthesis of non-carbon-centered chiral compounds under mild conditions has become very meaningful, and is still a great challenge. Herein, we break through the limitation of traditional asymmetric allylic alkylation reaction catalyzed by Lewis bases using MBH adduct as allylation reagent, in which the reaction of non-prochiral MBH adduct with heteroatomic nucleophilic reagent avoids the formation of chiral carbon during the bond forming, that realize the synthesis of non-carbon-centered chiral compounds. Furthermore, the application of the synthesized chiral compounds in asymmetric synthesis was also included in this project.