Methods for direct enantioselective oxidation of C(sp3)–H bonds will revolutionize the preparation of chiral alcohols and their derivatives. We present a copper-based biomimetic catalytic system that achieves highly efficient asymmetric sp3 C–H oxidation with C–H substrates as the limiting reagent. A Cu(II)-bound tert-butoxy radical is responsible for the site-selective C–H bond cleavage,  which resembles the active site of copper-based enzymes for C–H oxidation. The developed method has been successfully accomplished with good  functional group compatibility and exceptionally high site- and enantioselectivity, which is applicable for the late-stage oxidation of  bioactive compounds. This result is published in Nat. Catal. Congratulations Honggang Zhang.

Development of methods for the sp² C-H transformations of allenes has received much attention, and it presents a powerful tool for the synthesis of complicated allene-containing bioactive molecules. With a copper-catalyzed radical relay, the sp² allenic C-H arylation and alkynylation were established herein, using various aryl boronic acids and trimethoxysilyl-substituted alkynes as carbon nucleophiles, and using electrophilic N-F reagents as nitrogen-centered radical precursors. These methods featured excellent site-selectivity to deliver fully substituted allenes efficiently. Moreover, with silyl-substituted allenes as substrates, a subsequential dual sp² C-H functionalization process was established as well, which allowed for the divergent synthesis of multi-functionalized allenes, significantly expanding their chemical spaces. This result is published in JACS. Congratulations Zhongming Cheng.