Having established a novel methodology for the asymmetric cyclization of sevenmembered rings via SNAr, we set out to explore whether this preorganization strategy and catalyst control was generalizable to other ring sizes and, potentially, to other mechanistic paradigms, given the preservation of key non-covalent interaction sites (Figure ). Replacing the nitroaryl fluoride moiety of 2a for a benzyl chloride, we prepared substrate 4a as a potential precursor to the homologated eight-membered ring product 5a (Figure ). Excitingly, the intramolecular SN2 reaction took place quickly and with perfect intramolecular selectivity to afford dibenzodiazocinone 5a, which also proved to be inherently chiral and configurationally stable (ΔG ‡ rac, 5a, 348 K = 27.5 kcal/mol, t1/2, 5a, 25 °C ~ 200 days, see Table ). Once again, we observed no formation of oligomeric products. This reaction also translated well to catalytic conditions, and we were excited to observe that the same catalyst 1d could induce high degrees of enantioselectivity in the formation of eight-membered ring products. The SNAr lead catalyst 1d also proved to be the most selective for the SN2 reaction and delivered product 5a in 98% yield and 96:4 er under optimized conditions (see Figure for more catalyst screening data). Under the same conditions, we were able to prepare a series of inherently chiral dibenzodiazocinones in high yields and selectivity, with both peripheral and internal substitution being well tolerated (Figure ). Preparation of an enantioenriched nine-membered ring analog was also attempted (5g, Figure ). While bond formation proceeded smoothly, we observed no enantioselectivity, perhaps due to the lower enantiomerization energy barrier of the larger ring size.