Diastereoselective Functionalization of sp3 C-H Bonds

描述（由申请人提供）：C-H键的官能化具有从根本上改变有机合成实践并使其更有效的巨大希望。虽然最近的进展已经开始认识到其潜力，将需要更多的发展，特别是在该地区的非对映选择性功能化的sp3 C-H键。该提案详细说明了关于使用螯合基团来直接Pd或Rh催化活化sp3 C-H键的方法。底物内预先存在的手性将用于偏置C-H活化的非对映选择性。将在三种类型的反应中探索所得的非对映体富集的环状络合物：1）经由Suzuki或Hiyama偶联的碳-碳形成; 2）Pd π-烯丙基络合物的区域选择性烷基化; 3）与双（频哪醇合）二硼的硼基化。本文所讨论的三种反应将作为一个平台，探讨如何控制非环底物C-H官能化的非对映选择性的因素。每种类型的反应也可以以互补的方式与当前的羟醛缩合方法、Pd π-烯丙基化学和巴豆基金属技术一起应用。

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.