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序，具有独特的生物活性。然而，迄今为止，只有很少的方法用于（对映体）选择性地构建四元全碳取代的立体中心。最近，Stoltz教授的团队可以开发一种新的策略来访问这种具有挑战性的结构基序。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。此外，后续的转化所获得的产品将进行调查，以提高灵活性和适用性的调查方法。最后，开发的方法将实施到天然存在的倍半萜herbertenediol和enokipodin A的合成和生物碱mesemrin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.