Chiral amine N-oxides feature an electron-donating oxygen atom in the N + -O -group and have proved to be effective ligandsand organocatalysts in asymmetric catalysis since 1993. For example, Nakajima, Hayashi, Takenaka and coworkers reported the use of biquinoline/pyridine N,N-dioxides as catalytic ligands for the asymmetric allylation of aldehydes and conjugate additions of thiols. 2 However, the application of chiral N-heteroaromatic N-oxide ligands in asymmetric catalytic reactions for different reaction types and substrates is still limited. It was not until Feng's group developed a new family of C2-symmetric N,N ′ -dioxide amides from readily available chiral amino acids insensitive to moisture and air demonstrated to be privileged by their applications in more than 70 types of asymmetric reactions not only as organocatalysts. Recently, Guo, Xie and co-workers have developed a new class of chiral DMAP-derived N-oxides as e ffi cient organocatalysts. In addition, Liu and co-workers invented a novel family of tertiary amine-derived C2symmetric chiral pyridine-N,N ' -dioxide ligands (Py-2NO) applied in Friedel-Crafts reaction affording the corresponding adducts in excellent yields and enantioselectivity. Although the previous research has left a deep impression on us, not all existing ligands could meet every reaction, so the development of novel type of highly efficient chiral C2-symmetric Ndioxides catalysts was still needed. Inspired by previous research and combined with our experience in developing chiral-at-metal Rh(III) complexes, 6 herein we designed and synthesized a new tetradentate C2-symmetric chiral bipyridine-N,N,-dioxides ligand and successfully applied them to synthesize chiral pyrazolo [3,4-b]pyridine analogues (Scheme 1). 7