Communications
Table 1: Selected physical data of compounds 3, 4, 6, 9, 10, 12, 13, 24,
and 26.[a]
3:[b] White crystals; m.p. 149–1518C (CH3OH or CH2Cl2); major isomer:
1H NMR ([D6]DMSO): d=1.34 (s, 6H, CH3), 2.36 (d, 3J=8.1 Hz, 2H,
NH), 2.58 ppm (d, 3J=8.1 Hz, 2H, NH); 13C NMR ([D6]DMSO):
d=19.71 (q, CH3), 56.51 ppm (s, C-3); 15N NMR ([D3]MeNO2, also as
standard with d=0): d=À314.8 (d, 1J=64 Hz), À308.9 ppm (d,
1J=62 Hz); minor isomer: 1H NMR ([D6]DMSO): d=1.31 (s), 2.42 ppm
(br); 13C NMR ([D6]DMSO): d=20.52 (q), 56.22 ppm (s).
1
4: Pale yellow crystals; m.p.=56–588C; H NMR ([D6]DMSO): d=0.98
(s, 3H, CH3), 1.13 (s, 3H, CH3), 2.57 (d, J=8.1 Hz, 1H, NH), 2.68 ppm
(d, J=8.1 Hz, 1H, NH); 13C NMR ([D6]DMSO): d=15.28 (q, CH3), 19.95
(q, CH3), 28.04 (s, C-3), 54.45 ppm (s, C-3’).
6: Brown oil; IR (C6D6): n˜ =2963, 2928, 1580, 1436, 1384, 1103 cmÀ1
;
1H NMR (CDCl3): d=0.85 ppm (s, CH3); 13C NMR (CDCl3): d=15.30 (q,
CH3), 26.55 ppm (s, C-3); 15N NMR (CDCl3): d=69.7 ppm.
9:[b] Yellow crystals; m.p. 120–1258C (hexane/Et2O); major isomer:
1H NMR ([D6]DMSO): d=1.50–1.85 (m, 10H, CH2), 2.37 (d, 3J=8.1 Hz,
2H, NH), 2.60 ppm (d, 3J=8.1 Hz, 2H, NH); 13C NMR ([D6]DMSO):
d=23.59 (t), 26.69 (t), 34.10 (t), 59.09 ppm (s); minor isomer: 1H NMR
([D6]DMSO): d=1.50–1.85 (m, 10H, CH2), 2.01 (d, 3J=7.8 Hz, 2H,
NH), 2.59 ppm (d, 3J=7.8 Hz, 2H, NH); 13C NMR ([D6]DMSO):
d=25.26 (t), 29.26 (t), 35.75 (t), 57.92 ppm (s).
10:[b] Brown solid; m.p. 152–1548C; IR (KBr): n˜ =3427, 3178, 2946, 2923,
2863, 2366, 1652, 1399, 1201, 855 cmÀ1; 1H NMR ([D6]DMSO): d=1.62
(brs, 8H, CH2), 2.23 (d, 3J=7.8 Hz, 2H, NH), 2.63 ppm (d, 3J=7.8 Hz,
2H, NH); 13C NMR ([D6]DMSO): d=24.14 (t), 33.79 (t), 58.06 ppm (s).
12: Brown oil; 1H NMR (CDCl3): d=1.30 (m, 4H, CH2), 1.70–1.86 ppm
(m, 6H, CH2); 13C NMR (CDCl3): d=24.43 (t), 29.91 (s, C-3/C-4), 30.29
(t, C-9), 32.84 ppm (t).
Scheme 3.
20 (25–35%) were obtained when trapping reagent 16 was
added after photolysis of 12 at low temperature (À908C in
CD2Cl2 or À1208C in CD2ClF).
13: Brown oil; 1H NMR (CDCl3): d=1.36 (m, 4H, CH2), 1.86 ppm (m,
4H, CH2); 13C NMR (CDCl3): d=23.72 (t), 27.99 (s), 30.68 ppm (t).
24:[b] Yellow oil; IR (CDCl3): n˜ =3176, 3124, 2970, 2878, 1670, 1591, 1406,
The bisimine 23, which is easily accessible from diketone
22, can also be transformed into bidiaziridines. After workup
1
1125 cmÀ1; H NMR (CDCl3): d=1.05–2.55 (m), 2.60–3.80 ppm (m);
13C NMR (CDCl3): d=23.51 (t), 24.95 (t), 34.77 (t), 43.00 (d), 43.20 (d),
64.34 (s), 64.79 ppm (s).
26: Brown oil; 1H NMR (CDCl3): d=1.50 (m, 2H, 7-H/10-H), 1.54 (dt,
2J=9.9 Hz, 4J=1.8 Hz, 1H, 11syn-H), 1.75 (m, 2H), 2.02 (m, 2H),
2.37 ppm (dm, 2J=9.9 Hz, 1H, 11anti-H); 13C NMR (CDCl3): d=24.53 (t,
C-8/C-9), 37.28 (t, C-11), 37.88 (s, C-3/C-4), 40.19 ppm (d, C-7/C-10).
[a] 1H NMR: 300 MHz; 13C NMR: 75 MHz; 15N NMR; 30 MHz. [b] The
bidiaziridines 3, 9, 10, and 24 were treated with an excess of PhNCO to
yield urea derivatives which were completely characterized (including
combustion analyses).
The spirocyclic diaziridines 9 and 10 were accessible from
the bisimines 8[14] and 11a[14] or 11b,[15] respectively. The
spectroscopic data of 9 (Table 1) point to a mixture of
diastereomers (ca. 9:5). The isolable title compounds 12 and
13, which function as precursors of cycloheptyne (1a) and
cyclohexyne (1b), were obtained by oxidation of 9 and 10,
respectively. When 12 or 13 were warmed in the presence of
the reaction partners 14, 15, or 16, the trapping products of
cycloalkynes 17–21[16] were formed in excellent yields
(Scheme 3). Similar results were achieved on irradiation of
precursors 12 or 13 in the presence of 14 or 16. Lower yields of
Scheme 4.
310
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 309 –311