Diastereoselective Functionalization of sp3 C-H Bonds

描述（由申请人提供）：碳氢键的功能化有望从根本上改变有机合成的实践，并使其更高效。虽然最近的进展已经开始认识到它的潜力，但在sp3碳-氢键的非对映选择功能化方面还需要更多的发展。该建议详细介绍了使用螯合基团来指导Pd或Rh催化活化sp3 C-H键的方法。在底物内预先存在的手性将被用来偏置C-H活化的非对映选择性。所得到的非对映体富集环金属配合物将在三种类型的反应中进行探索：1)通过Suzuki或Hiyama偶联形成碳-碳；2) Pd -烯丙基配合物的区域选择性烷基化反应；3)与双（pinacolato）二硼的硼化。本提案中讨论的三种类型的反应将作为一个平台，探讨如何控制非环底物C-H功能化中的非对映选择性。每种类型的反应也可以与当前的醛醇方法、Pd -烯丙基化学和丁基金属技术互补应用。

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.