Asymmetric Pd-Catalyzed Conjugate Addition of Boronic Acids to Acceptor-Substituted Olefins - An Enantioselective Access to All-Carbon Quaternary Stereocenters

四元全碳取代立体中心是复杂天然产物中常见的结构基元，往往具有不同的生物活性。然而，到目前为止，只有很少的方法(对映体)选择性地构建了四元全碳取代的立体中心。最近，斯托尔茨教授的团队可能开发出一种新的策略来理解这一具有挑战性的结构主题。拟议研究提案的目标是通过调查替代反应伙伴和优化已被证明是复杂的底物的使用来进一步改进方法学。此外，还将对所获得产品的后续转化进行调查，以提高所调查方法的灵活性和适用性。最后，将所开发的方法学应用于天然倍半萜类化合物Herbertendiol和Enokipodin A的合成以及生物碱中膜蛋白的合成。

Quarternary all-carbon substituted stereocenters are a common structural motif in complex natural products which often show distinct biological activities. However, only few methods for the (enantio-) selective construction of quarternary, all-carbon substituted stereocenters have been developed so far. Recently, the group of professor Stoltz could develop a new strategy to access this challenging structural motif. The goal of the proposed research proposal is to further improve the methodology by investigating alternative reaction partners and optimizing the use of substrates that have been shown to be complicated. In addition, subsequent transformations on the obtained products will be investigated in order to improve the flexibility and applicability of the investigated methodology. Finally, the developed methodology will be implemented into the synthesis of the natural occuring sesquiterpenes herbertenediol and enokipodin A and in the synthesis of the alkaloid mesembrin.