Novel design of 3,8-diazabicyclo[3.2.1]octane framework in oxidative sulfonamidation of 1,5-hexadiene

Oxidative cycloaddition of electron-deficient arenesulfonamides to hexa-1,5-diene

“…2). Unlike cis-2,5bis(iodomethyl)-1-tosylpyrrolidine studied previously [1], the iodomethyl substituents in molecule 7 are arranged trans. The N 1 S 1 C 3 angle is 107.05°, which is close to the corresponding angle in analogous struc- (7) according to the X-ray diffraction data.…”

“…No bicyclic products analogous to 3,8-bis(trifluoromethanesulfonyl)-3,8-diazabicyclo[3.2.1]octane (which was formed together with the corresponding trans-pyrrolidine in the reaction of trifluoromethanesulfonamide hexa-1,5-diene [1]) were detected in the reaction mixtures obtained from arenesulfonamides 2 and 3. We also found that cis isomers 4 and 6 whose steric structure is favorable for the cyclization into 3,8-diazabicyclo[3.2.1]octanes do not react with trifluoromethanesulfonamide under the examined conditions.…”

“…Stereoselective formation of cis-substituted N-sulfinyl- [21] and N-sulfonyl-2,5-disubstituted pyrrolidines [22] was observed when the initial sulfinyl-(sulfonyl)amino alkene possessed a chiral center in the γ-or β-position with respect to the double bond (Scheme 5). In the present work we examined reactions of hexa-1,5-diene (1) with electron-deficient arenesulfonamides 4-XC 6 H 4 SO 2 NH 2 [X = NO 2 (2), Cl (3)] in the oxidative system t-BuOCl-NaI with a view to comparing the results with our previous data for the reactions of diene 1 with trifluoromethanesulfonamide, p-toluenesulfonamide, and benzenesulfonamide under analogous conditions [1]. In particular, it was interesting to find out whether most electron-deficient arenesulfonamide 2 would react like trifluoromethanesulfonamide, i.e., with formation of a bicyclic product, disubstituted…”

“…In contrast, benzenesulfonamide and p-toluenesulfonamide reacted with hexa-1,5-diene to give a mixture of cis-and transisomeric 2,5-bis(iodomethyl)-1-(arenesulfonyl)pyrrolidines but no bicyclic products were detected [1]. Further development of methods for the synthesis of substituted pyrrolidines is worthy taking into account practical importance of these compounds.…”

“…We have reported previously that the reaction of hexa-1,5-diene with trifluoromethanesulfonamide in the oxidative system t-BuOCl-NaI yields a mixture of trans-2,5-bis(iodomethyl)-1-(trifluoromethanesulfonyl)pyrrolidine and 3,8-bis(trifluoromethanesulfonyl)-3,8-diazabicyclo[3.2.1]octane [1]. In contrast, benzenesulfonamide and p-toluenesulfonamide reacted with hexa-1,5-diene to give a mixture of cis-and transisomeric 2,5-bis(iodomethyl)-1-(arenesulfonyl)pyrrolidines but no bicyclic products were detected [1].…”