We observed adding LiHMDS to a THF solution containing only nitropyridine 2a led to decomposition to an intractable mixture of products. Therefore, we examined the effect of order of addition by carrying out the reaction in two ways: In Method 1, LiHMDS was added dropwise to a solution of aniline 1b and nitropyridine 2a at room temperature in an open flask. In Method 2, LiHMDS was added dropwise to a solution of 1b cooled to -78 °C under an inert atmosphere, and then a solution of 2a was added dropwise. The isolated yields from both methods were identical (50%, Scheme S2). We therefore believe that the deprotonation and subsequent reaction of aniline 1b with 2a is faster than the base-mediated decomposition of 2a. With the optimized conditions developed, we then explored the substrate scope of nitro(hetero)arenes and nucleophiles in the LiHMDS-promoted ONSH amination reaction (Scheme 3). We began our investigations varying the amine component using primary anilines and found that 4-chloro and unsubstituted anilines cleanly provided the desired products 5a,b in moderate yield. We next tested the toluidine series 5c-e and were surprised to find that ortho-substitution was well tolerated: 2-toluidine provided the 2-methyl-substituted 5c in similar yield to the 3-methyl and 4-methyl isomers 5d,e. In contrast, the yield of the product arising from 2-chloroaniline 5g was reduced relative to the 3-chloro and 4-chloro isomers 5f,a. Electron-rich panisidine and 3,4-dimethoxyaniline formed 5h and 5i respectively in reduced yields compared to the electron-neutral aniline that delivered 5b. The secondary N-methylaniline performed poorly to give 5m in low yield, possibly due to steric effects. The doubly ortho-substituted and quite electron-poor 2,3,5,6tetrafluoroaniline impressively provided the hindered product 5n, albeit in lower yield. Heteroaryl amines such as pyrazolamines, isoquinolinamines, and pyridinamines were tolerated 5o-t. Notably, 2-fluoropyridin-4-amine gave a clean crude UPLC/MS trace and afforded the ONSH product 5t in 35% yield after chromatography; no competitive SNAr was observed. Phenols and aliphatic amines were tested but did not deliver any ONSH product.