In 2016, Ohmiya and Sawamura described the construction of quaternary stereogenic carbon centers through Cucatalyzed enantioselective allylic alkylation of azoles. The reaction proceeded through a LiOtBu-assisted cupration of acidic azole C-H bond, which doesn't involve the formation of chiral C-Cu species. Recently, Duan and coworkers disclosed the asymmetric C-H arylation with diaryliodonium salts enabled by Cu/bisoxazoline system. However, the scope was limited to specific electron-rich (hetero)arenes, since the reaction mechanically proceeded through the electrophilic cupration. Since the pioneering works by the Yu and Chatani groups in 2006, copper-catalyzed/mediated C-H activation assisted by directing groups (DGs) is burgeoning, especially by the assistant of strongly coordinating bidentate DGs. However, the enantioselective version is still underdeveloped. In 2018, Yu and Dai elegantly introduced a chiral oxazoline amide as directing group to achieve copper-mediated diastereoselective C-H thiolation reactions. Very recently, during the preparation of this manuscript, Yu and Wang disclosed the enantioselective C-H alkynylation using stoichiometric copper salts. This breakthrough highlighted the potential of copper catalysis, however, the reaction is limited to the use of stoichiometric amount of copper salts, and unsatisfactory selectivity (1.5:1 to 10:1 mono:di; 76%-86% ee). In continuation of our long-term interest in copper-catalyzed C-H activation and 3d metal-catalyzed enantioselective C-H activation, we have long pursued to establish an efficient strategy that proceeded through the formation of a chiral C-Cu intermediate, which could be divergently transferred to various C-C and C-X bonds that is inaccessible through outer-sphere mechanism. However, the establishment of such a protocol is highly challenging due to several inherent properties of Cu-catalyzed/mediated C-H activation reactions: 1) The coordination pattern and valence of copper intermediates during the whole reaction is unclear, because of the easily accessible oxidation states (from 0 to +3); 2) Cu-catalyzed/mediated C-H activation reactions largely rely on the use of strongly coordinating directing groups, which could act as stoichiometric ligands to compete with catalytic chiral ligands, leading to strong background reaction; 3) The need of extremely high temperature (generally >130 o C) and selectivity between mono-