With the optimized catalyst and conditions, we first investigated the reactivity and selectivity of different aromatic nitriles in the process (Fig. ). In this respect, both electron-donating groups (-OMe, -NMe2) and electron-withdrawing groups (-CF3, -F) were accommodated, providing the corresponding pyridines 8a to 8e in high yields and enantioselectivities. The process is mild and displays a good functional group tolerance, allowing incorporation of ester, pinacol boryl, chloro-, and vinyl groups as substituent on the nitriles (8f to 8i). Similarly, reactions with aliphatic nitriles including acetonitrile, phenyl acetonitrile, valeronitrile, cyclopropanecarbonitrile, and 3methoxy propionitrile provided pyridines 8j-8n in high enantioselectivities. X-ray crystallographic analysis of pyridine 8m allowed determination of its absolute configuration. Hept-6-ene-nitrile possessing a terminal olefin moiety cleanly gave 8o in 88% yield and a 98:2 er with no chain-walking products involving the olefin detected. (39) Electron-rich heteroaromatic nitriles such as 3-cyanothiophene and N-Me-2-cyano pyrrole yielded pyridines 8p (90% and 98.5:1.5 er) and 8r (73% and 97:3 er). 2-Cyanopyridine as example for an electron-poor heterocycle is particularly noteworthy that product 8q features the sought-after 2,2'-bipyridine motif. Cyano ferrocene was also effectively accommodated without catalyst poisoning or side-product formation. Concerning the alkyne pattern, ethyl substituents resulted in a similar outcome (8u). The challenging terminal dialkyne produced the desired desymmetrization product 8t, albeit in somewhat reduced enantioselectivity. Functionalized bis-1,4-enyne 1i and bis-1,3-enyne 1k engaged in the hetero [2+2+2] cycloaddition yielding bis-olefin bearing pyridines 8v and 8w that could be exploited for subsequent polymerization reactions. Variations on fluorene core substituent R 1 include different aryl groups (8y and 8z) and a bis-PMP amino group (8x) that has prominent appearances in spirofluorene materials. 40 Notably, installing a pinacol boryl group at R 1 gave pyridine 8aa which can act as broadly diversifiable intermediate via a variety of cross-couplings. Next, we aimed to explore the suitability of enantioselective hetero [2+2+2] cycloaddition for generating spiro heteroatom chirality. In this respect, an extension of the process to chiral tetra-coordinated boron compounds focusing on the aza-borafluorene was initially followed. Pleasingly, under same reaction conditions Ni3 displayed a robust performance and delivered pyridine derivatives 9a and 9b with their boron stereogenic centers in excellent yields and very good enantioselectivity. A slight erosion of selectivity was found for products 9c and 9d which have a relatively smaller substituent R 5 . Interestingly, the effect of the distorted tetrahedral geometry of the boron starting material manifests itself by different selectivities of substrates that are identical besides having the bis-phenyl amino substituent on the phenyl ring (9e) or on the pyridine ring (9b), with the former providing a superior enantiomeric ratio. As for the previous carbon series, a diverse range of nitriles, including aromatic, aliphatic and heteroaromatic nitriles, was found to be compatible leading to corresponding chiral spiro boron compounds 9e to 9g in excellent enantioselectivities. 1-(4-(tBu)phenyl)isoquinoline-based boron dialkyne substrate 3g displaying a complex steric environment yielded pyridine 9h in 84% yield and 95:5 er. A further extension was reached with N,N'-chelated boron scaffolds. (43) These pyridyl pyrrolide chelated boron substrates were amenable to the transformation and the corresponding spirocyclic tetra-coordinated boron compounds 9i and 9j were formed in excellent yield and moderate to good selectivities. Our focus shifted next to the selective construction of chiral spirogermanium center. Using germafluorene 9 5a (R 1 =Ph) as a starting material provided spiro germafluorene 10a in 85% yield albeit in virtually racemic form. Since phenyl as R 1 substituent was highly selective in the carbon as well as in the boron series, we attribute this lack of selectivity as direct result of the longer C-Ge bond length and its induced distortion of the center and altered vector of R 1 . However, the selectivity of the transformation was restored with substrate 5b (R 1 =tBu) leading to spiro germafluorene 10b in 91% yield and 80:20 er. Furthermore, the reaction of 5c (R 1 =trityl) yielded compound 10c increased in 95% yield and an increased er of 86:14. Surprisingly, exposure of silicon-based analogues 4a and 4b to the reaction conditions caused substrate decomposition and the formation of pyridine products was not observed.