Synthesis of Enantiopure 2‐Alkyl‐1,3,3‐Trinitroazetidines

Enantiopure 2‐alkyl‐1,3,3‐trinitroazetidines 4 were efficiently synthesized by the nitrolysis of enantiopure 2‐alkyl‐3,3‐dinitro‐1‐tosylazetidines 3 using an excess of fuming nitric acid in CHCl 3 at ambient temperature. In addition, elaboration of ( S )‐2‐(2‐methoxyethyl)‐1,3,3‐trinitroazetidine ( 4c ) was successfully performed to synthesize a variety of enantiopure 2‐alkyl‐1,3,3‐trinitroazetidines 5 – 7 . The advantage of this strategy is that 2‐alkyl‐1,3,3‐trinitroazetidines can be synthesized either asymmetrically or racemically depending on the presence or absence of chirality in N ‐sulfinyl aldimines 2 used as the starting material. Furthermore, the sensitivity measurement results of racemic 2‐methyl‐1,3,3‐trinitroazetidine (racemic 4a ) showed that the introduction of an alkyl substituent at the C2 position of 1,3,3‐trinitroazetidine had a significant effect on the sensitivity of the resulting 2‐alkyl‐1,3,3‐trinitroazetidine.