T. Olszewska et al. / Tetrahedron: Asymmetry 16 (2005) 3711–3717
3715
J = 13.2 and 2.4 Hz, 1H), 2.86 (dt, J = 12.7 and 2.4 Hz,
4.6. N-Thioformyl-3-azabicyclo[3.3.1]nonane 3b
1H), 1.74 (m, 3H), 1.20 (m, 2H), 0.95 (d, J = 6.4 Hz, 3H);
13C NMR (CDCl3) d 184.8, 54.9, 44.2, 33.9, 32.1, 29.9,
20.6. Complex with 4b: mp 111–112 °C. Anal. Calcd
for C33H32O4ÆC7H13NS(634): C, 75.80; H, 6.84; N,
2.21; S, 5.06. Found: C, 75.50; H, 7.12; N, 2.17; S, 4.90.
Formamide 3a was obtained by formylation 3-azabi-
cyclo[3.3.1]nonane17 in a similar manner to that of
compound 1a as a colourless oil; 1H NMR (CDCl3)
d 7.97 (s, 1H), 4.33 (d, J = 13.2 Hz, 1H), 3.57
(d, J = 12.7 Hz, 1H), 3.37 (d, J = 12.7 Hz, 1H), 2.86
(d, J = 13.2 Hz, 1H), 1.90 (bs, 2H), 1.80–1.58 (m, 7H),
1.43 (m, 1H); 13C NMR (CDCl3) d 162.3, 52.1, 46.0,
33.8, 31.1, 30.6, 28.1, 27.4, 20.2.
4.3. N-Selenoformyl-4-methylpiperidine 1c
Amide 1a (1.0 g, 7.9 mmol), powdered selenium (0.6 g,
19 mmol), red phosphorus (0.6 g, 19 mmol) and BaCO3
(1.0 g, 5.1 mmol) were refluxed in xylene (30 mL) for
24 h. After cooling, the reaction mixture was filtered
and the precipitate washed with benzene. Evaporation
of the solvents at a reduced pressure afforded 1.1 g
(74%) of the product as a yellow oil, solidifying upon
Thioamide 3b was obtained from formamide 3a in a
similar manner to that of compound 1b; mp 129–
131 °C; IR (KBr) 1510, 1241, 1104 cmꢀ1 1H NMR
;
(CDCl3) d 9.19 (s, 1H), 5.18 (d, J = 14.2 Hz, 1H), 3.81
(d, J = 12.7 Hz, 1H), 3.73 (d, J = 13.2 Hz, 1H), 3.01
(dd, J = 13.7 and 2.9 Hz, 1H), 2.10 (s, 1H), 2.01 (s,
1H), 1.90–1.60 (m, 7H), 1.50 (m, 1H); 13C NMR
(CDCl3) d 187.5, 61.8, 51.2, 33.5, 31.4, 30.7, 29.2, 28.6,
20.0. Anal. Calcd for C9H15NS(169): C, 63.90; H,
8.86; N, 8.28; S, 18.93. Found: C, 63.86; H, 8.99; N,
8.22; S, 18.84.
refrigeration; IR (film) 1516, 1454, 1228 cmꢀ1
;
1H
NMR (CDCl3) d 10.59 (s, 1H), 5.29 (dt, J = 13.1 and
2.0 Hz, 1H), 3.81 (dt, J = 12.9 and 2.0 Hz, 1H), 3.38
(td, J = 12.8 and 2.6 Hz, 1H), 2.89 (td, J = 12.8 and
2.8 Hz, 1H), 1.79 (m, 3H), 1.29 (m, 2H), 0.99 (d,
J = 6.2 Hz, 3H); 13C NMR (CDCl3) d 186.9, 57.8,
47.9, 33.8, 32.1, 29.8, 20.5; 77Se NMR (CDCl3) d 498.0.
4.7. N-Selenoformyl-3-azabicyclo[3.3.1]nonane 3c
Complex with 4b: mp 110–112 °C. Anal. Calcd for
C33H32O4ÆC7H13NSe (681): C, 70.58; H, 6.37; N, 2.06.
Found: C, 70.30; H, 6.31; N, 2.01.
Compound 3c was obtained from formamide 3a in a
similar manner to that of compound 1c; mp 143–
144 °C; IR (KBr) 1507, 1436, 1235 cmꢀ1 1H NMR
;
4.4. N-Thioformyl-1,5-dimethyl-3-azabicyclo[3.l.0]hexane
2b
(CDCl3) d 10.59 (s, 1H), 5.30 (d, J = 14.2 Hz, 1H),
3.83 (d, J = 13.2 Hz, 1H), 3.61 (d, J = 12.7 Hz, 1H),
3.00 (d, J = 14.2 Hz, 1H), 2.15 (s, 1H), 2.02 (s, 1H),
1.90–1.60 (m, 7H), 1.50 (m, 1H); 13C NMR (CDCl3)
d 189.9, 64.4, 54.6, 33.2, 31.3, 30.6, 29.3, 28.8, 19.9;
77Se NMR (CDCl3) d 535.1. Anal. Calcd for C9H15NSe
(216): C, 50.00; H, 6.94; N, 6.48. Found: C, 50.42; H,
7.10; N, 6.43.
Formamide 2a was obtained by formylation of 1,5-
dimethyl-3-azabicyclo[3.l.0]hexane16 in a similar manner
1
to that of compound 1a; bp 100–106 °C/12 mmHg; H
NMR (CDCl3) d 8.03 (s, 1H), 3.82 (d, J = 11.5 Hz,
1H), 3.52 (d, J = 10.1 Hz, 1H), 3.30 (d, J = 10.1 Hz,
1H), 2.94 (d, J = 11.5 Hz, 1H), 1.11 (s, 3H), 1.10 (s,
3H), 0.36 (d, J = 5.1 Hz, 1H), 0.23 (d, J = 4.9 Hz, 1H);
13C NMR (CDCl3) d 160.8, 53.8, 50.4, 24.1, 19.4, 14.3.
4.8. Preparation of the crystalline inclusion compounds
A solution of the suitable host compounds 4a and b with
the respective racemic thioamides 1b–3b or selenoamides
1c–3c in a small amount of toluene–hexane (1:2) was
kept at room temperature for 4 h. The crystals, which
formed, were collected by suction, washed with hexane
and dried. Host–guest stoichiometry was determined
Thioamide 2b was obtained from formamide 2a in a
similar manner to that of compound 1b; mp 49–50 °C;
IR (KBr) 1503, 1218, 971 cmꢀ1 1H NMR (CDCl3)
;
d 9.20 (s, 1H), 4.30 (d, J = 13.3 Hz, 1H), 3.80
(d, J = 11.3 Hz, 1H), 3.66 (d, J = 11.3 Hz, 1H), 3.27 (d,
J = 13.3 Hz, 1H), 1.22 (s, 3H), 1.19 (s, 3H), 0.47 (d,
J = 5.3 Hz, 1H), 0.40 (d, J = 5.1 Hz, 1H); 13C NMR
(CDCl3) d 184.6, 60.8, 55.7, 24.4, 20.5, 13.9. Anal. Calcd
for C8H13NS(155): C, 61.89; H, 8.44; N, 9.02; S, 20.65.
Found: C, 61.93; H, 8.50; N, 8.93; S, 20.37.
1
by H NMR integration.
4.9. X-ray structure analysis
Diffraction data were collected using a Kuma CCD
4.5. N-Selenoformyl-1,5-dimethyl-3-azabicyclo[3.l.0]-
hexane 2c
diffractometer with graphite monochromated Mo Ka
˚
radiation (k = 0.71073 A). The structures were solved by
direct methods with the program SHELXS-97.18 Full
matrix least-squares refinement was carried out with
SHELXL-97.19
Compound 2c was obtained from formamide 2a in a
similar manner to that of compound 1c as an orange
oil; IR (film) 1503 cmꢀ1 1H NMR (CDCl3) d 10.58
;
(s, 1H), 4.30 (d, J = 13.6 Hz, 1H), 3.68 (d,
J = 11.7 Hz, 1H), 3.48 (d, J = 11.7 Hz, 1H), 3.21 (d, J =
13.6 Hz, 1H), 1.22 (s, 3H), 1.17 (s, 3H), 0.47 (d,
J = 5.4 Hz, 1H), 0.40 (d, J = 5.3 Hz, 1H); 13C NMR
(CDCl3) d 186.3, 62.9, 58.7, 24.6, 20.5, 13.9; 77Se
NMR (CDCl3) d 592.6.
Crystal data for C33H32O4ÆC7H13NS( 1bÆ4b): triclinic,
P1, a = 9.4983(6), b = 9.7270(7), c = 18.8808(12) A,
˚
a = 98.495(5), b = 93.921(5), c = 90.892(5)°, V =
3
1720.6(2) A , Z = 2, Dcalcd = 1.287 g cmꢀ3, T = 100(2) K,
˚
R1 = 0.0635, wR2 = 0.0806 for 5823 reflections with
I > 2r(I).