Anilines/amines In most cases this delivered the anti-chloroamine product as a single diastereomer. The anti-chloroamine could then be treated with LiHMDS to deliver the desired cis-aziridine with complete stereochemical fidelity (Scheme 5b). Regarding the generality of the two-step process, a range of heterocycles and aromatic amines were compatible. For the conjugate addition step (Scheme 5a), modification of the azaheterocycle was possible, with substituted quinoline cores achieving moderate to excellent yields (13-16). In general, more electron-rich systems, such as those bearing electron-donating groups (16) or benzothiazole (17) were less reactive. Under the PhMe-based conditions, product ratio does not vary greatly from 1.2:1; however, except for benzothiazole 17, the enrichment process generally delivered >20:1 d.r. A broad range of anilines was accommodated, with efficiency varying in line with electronic parameters. Electron-rich anilines (e.g., 2-OMe, 18) were generally more efficient, due to enhanced nucleophilicity. Conversely, anilines bearing electron-withdrawing groups (e.g., 2-CF3, 20) performed poorly for the same reason. The incorporation of synthetic handles, such as halogens (22, 23, 26) or Bpin (19) was also tolerated with good yields. Scalability of this first step was demonstrated in a 4 mmol reaction of the benchmark reaction to give 0.45 g of 4 as a single diastereomer. The chloroamine products underwent smooth conversion to the desired cis-aziridines in generally excellent yields. Confirmation of stereochemistry was obtained through single crystal X-ray structures of 12 and 45. Scalability was also demonstrated in the benchmark reaction to give 0.37 g of 12 as a single diastereomer. There are some limitations to the route outlined, as shown in Scheme 5c (see ESI for full details). Alternative heterocycles, such as pyridine, pyrimidine, or benzimidazole systems were unreactive. The reaction was highly sensitive to amine nucleophilicity, with more nucleophilic amines (e.g., alkylamines) resulting in catalyst deactivation. In addition, anilines with strong electron-withdrawing groups, such as nitrile or ester, were also unreactive. Derivatization of the alkene substituent was also challenging (Scheme 6). Changing from Me (3) to Ph (1), i-Pr (48), or c-Hex (50) was not accommodated. Increasing catalyst loading, temperature, aniline equivalents, or reaction time failed to enable the conjugate addition process using these chloroalkenes. Scheme 6. Substitution tolerance on the chloroalkene component. Yield determined by 1 H NMR using TCE as an internal standard.