We began our efforts by exploring the alkylation of benzoxazole with norbornene (nbe) using nickel catalysts. After screening several common chiral ligands for enantioselective nickel catalysis, we found that NHCs derived from commercially available chiral diamines provided appreciable enantioinduction while maintaining good reactivity. Upon optimization of the reaction conditions through variation of ligand structure, solvent, temperature, and additives (see supporting information), we set out to demonstrate the utility of this method by exploring the scope of heteroarenes (Scheme 2). The optimized conditions involve in-situ preparation of an active chiral catalyst via the use of 5 mol % L5•HBF4, KHMDS and Ni(COD)2. The process is tolerant of electron-neutral and electron-rich benzoxazoles substituted at various positions (1a-1f) to give the alkylation products with good yields and enantioselectivities. Selective functionalization of benzofurans were also observed for C2 C-H bonds leaving functional groups such as boronic esters intact (1g-1i). LLHT products were not observed when using 5-bromobenzofuran as substrate (1j), which could be attributed to the facile activation of C(sp 2 )-Br bond in the presence of low-valent nickel catalyst. Benzimidazoles previously studied by Ackermann and Ye for enantioselective cyclizations were also reactive in our intermolecular system. We showed that nbe reacted with N-Me and N-Ph benzimidazoles (1k, 1l) to yield the C-H functionalization products with a moderate control for the enantioselectivity at 60 °C (vide infra). Interestingly, a C5-alkylated 1,2,4-triazole was exclusively obtained regio-and enantioselectively despite the relatively more hindered environment (1m). Other nitrogen containing heteroaromatic rings including caffeine (1n) and 3-methylquinazolin-4(3H)-one (1o) also underwent efficient couplings to give the desired product in good yields and 90:10 and 87:13 e.r. respectively. All of alkylation products were obtained as a single, exocyclic diastereomer. Scheme 2. Enantioselective heteroaromatic C-H functionalization scope. Reactions were performed at 0.10 mmol scale and yields were reported for isolated products. a Reaction was carried out at 60 °C.