In addition to aryl bromides, vinyl bromides were incorporated as well in this reaction, leading to structually diverse chiral N-allyl indoles 4a-4f in 35-60% yields with 73-95% ee values. Remarkably, this modular alkenylation complements previously established metalcatalyzed indole N-allylations in that di-and trisubstituted allylic products bearing aryl and alkyl groups are readily accessed. Besides the C(sp 2 ) bromides, this catalytic C-C bond-forming reaction was also viable for C(sp) bromides-bromoalkynes 5. As shown in Table , the treatment of bromoalkynes 5 and Nalkenyl indoles 1 with 10 mol% NiI 2 as the catalyst, 15 mol% L*8 as the ligand at 0 o C could yield the corresponding chiral N-propargyl indoles 6 in mostly good yields (25-89%) and high levels of enantioselectivity (ee values of 80-97%). A variety of N-alkenyl indoles substituted at the 4-position (6b), 5-position (6c-6g), 6-position (6h-6j), and 7-position (6k, 6l) each underwent efficient hydroalkynylation to provide the corresponding products with uniformly high enantioselectivities. Of note, alkyl group at the C3-position of the indole scaffold was demonstrated being tolerated again (6m). With regard to medicinal chemistry applications, the generation of product 6g demonstrates tolerance of a pinacol boronate subunit under the conditions of catalytic enantioselective alkynylation. Additionally, more sterically hindered cisβ-substituted N-alkenyl indoles also successfully underwent C(sp 3 )-C(sp) bond-formation to deliever compounds 6o and 6p, respectively, as single regioisomers with reasonable yields and good enantioselectivities. Beyond the TIPS-substituted ethynyl bromide 5a, TBS-and 3 o alkylsubstituted ethynyl bromides 5b-5c proved to be viable coupling partners in this system, affordding the desired indole adducts (6q-6r) in 47-74% yields with excellent enantioselectivities.