Bi-and polycyclic syn-azo azide substrates H, 5, 14 and I, 15 -18,36,41 d, respectively, of varying rigidity and proximity (with the potential nitrene nitrogen atom in the TI plane of the azo function) are prepared in order to synthesize kinetically stabilized cis,cis-trialkyltriaziridines. R F G Chem. Ber. 124 (1991) 609-620 J2a,3 = 11.5; J2p,3 x 6 Hz; diazacycloheptene chair, A , , , (E) = 391 nm (103; sh), 386 (106) (in CH3CN)] is converted with triphenylph~sphine/CCl:~) into the (3P)-chloride 4 10.0; JSp.9 = 6 Hz; 6: &.,I = 4.35; J s U , 9 = 6.5, JSp,9 = 9.5 (91 Yo, m. p. 79 -80°C; J2K3 = 6; Jzp,3 = 9 Hz) with quasiequatorial orientation of the C1 substituent. Treatment of 4 with sodium azide in DMF (SO' C) yieldsin a reaction complicated by the intervention of the (3a)-chloride 8 -the yellowish crystalline (la,3P,Sa)-azide 5 [m.p. 70°C, 0 = 2085 cm-I (N3), 1558 (N=N)] featuring a UV/Vis spectrum [Amax (E) = 393 nm (77; sh), 388 (80; N =N), 288 (31; N3) (in CH3CN)]25) very similar to that of 3. The 'H-NMR spectrum manifests a clear preference for a diazacycloheptene chair with the N3 function being quasi-equatorial (J2a,3 = 12, J2p,3 x 6 Hz). For comparison, (3P)-azide 9 (J1,2p x 3.5, JZK3 = 6.5 Hz) is analogously prepared from 3 (as mesylate) via (3a)-chloride 8. The synthetic route to azo azide 14aZ6) starts from cisbenzene trioxide (10) and is patterned after earlier applica-1 J 2 4 6 4c, 8 9 Chem. Ber. 124 (1991) 609-620 21 22 29 30 J 23 24 31 32 / 25 26 J __c 35 36 a b c 0 NOH NOAc -X Chem. Ber. 124 (1991) 609-620 The Azo/Nitrene Route to cis,cis-Trialkyltriaziridines, 1 JZa,X3,4a) = 6.0; J1.?1~4p,s) = 1.5; JZp,3(3.4p, = 9.0; J21.2fi4v,41)J = 14.0.(158.6) Calcd. C 53.00 H 6.99 N 17.65 CI 22.35 Found C 53.18 H 6.98 N 17.70 CI 22.75 Chem. Ber. 124 (1991) 609-620