Diastereoselective Functionalization of sp3 C-H Bonds

描述(申请人提供)：C-H键的官能化很有希望从根本上改变有机合成的实践，使其更加有效。尽管最近的进展已经开始实现它的潜力，但还需要更多的发展，特别是在SP3C-H键的非对映选择性官能化方面。该建议详细介绍了使用螯合基团来指导Pd或Rh催化的SP3C-H键的活化的方法。底物中预先存在的手性将被用来偏置C-H活化的非对映选择性。由此得到的非对映异构体富集环金属络合物将通过三种类型的反应来探索：1)通过Suzuki或Hiyama偶联形成碳-碳；2)Pd皮烯丙基络合物的区域选择性烷基化；3)与双(Pinacolato)二硼的硼化反应。这三种类型的反应将作为一个平台，探讨如何控制非对映选择性的非对映选择性的C-H功能化的非环底物。每种类型的反应也可以与当前的羟醛方法、Pd皮烯丙基化学和巴豆基金属技术以互补的方式应用。

DESCRIPTION (provided by applicant): Functionalization of C-H bonds holds a great promise to fundamentally change the practice of organic synthesis and make it far more efficient. Although recent advances have begun to realize its potential, much more development will be needed especially in the area of diastereoselective functionalization of sp3 C-H bonds. This proposal details approaches about the use of a chelate group to direct Pd or Rh catalyzed activation of a sp3 C-H bond. The preexisting chirality within substrates will be used to bias the diastereoselectivity of C-H activation. The resulting diastereomerically enriched cyclometalled complexes will be explored in three types of reactions: 1) carbon-carbon formation via either Suzuki or Hiyama coupling; 2) regioselective alkylation of Pd pi-allyl complexes; 3) borylation with bis(pinacolato)diboron. The three types of reactions discussed in this proposal will serve as a platform to probe the factors about how to control diastereoselectivity in C-H functionalization of acyclic substrates. Each type of reaction can be also applied in a complementary fashion with current aldol methodologies, Pd pi-allyl chemistries, and crotylmetal technologies.