168
H. A. Dondas et al. / Tetrahedron 58 (2002) 161±173
(m, 5H, ArH), 5.42 (m, 2H, 2£CHvCH2), 4.85 (m, 6H,
OCH2 and 2£CHvCH2), 2.31 (t, 2H, J8.0 Hz,
Z-CH2CvN), 2.16 (t, 2H, J7.9 Hz, E-CH2CvN), 2.04
(m, 4H) and 1.57 (m, 4H,); m/z (%) 271 (M1, 1), 256(1),
230(5), 111 (27) and 91 (100).
5.3.14. 5-Oxodeca-1.9-diene oxime O-allyl ether 16. The
product (64%) was obtained as a colourless oil, bp 90±948C/
0.7 mm Hg. (Found: C, 75.0; H, 10.0; N, 6.7. C13H21NO
requires: C, 75.3; H, 10.2; N, 6.75%); d 6.0 (m, 1H,
OCH2CHvCH2), 5.80 (m, 2H, 2£CHvCH2), 5.25 (m,
2H, OCH2CHvCH2), 5.00 (m, 4H, 2£CH2vCH), 4.55 (d,
2H, J5.0 Hz, OCH2) and 2.40±1.60 (m, 10H, 5£CH2), m/z
(%) 207 (M1, 15), 1520(41), 138(58) and 136 (100).
5.3.10. cis-2-(4-Pentenyl)-6-[(phenylseleno)methyl]piper-
idine 13 and trans-2-(4-pentenyl)-6-[(phenylseleno)-
methyl]piperidine 14. Phenylselenyl bromide (0.87 g,
3.69 mmol) was added to a solution of oxime ether 11
(1 g, 3.69 mmol) in dry acetonitrile (10 mL). The resulting
solution was stirred at roomtemperature for 16 h. Aceto-
nitrile was removed under reduced pressure and the residue
was taken up in DCM±MeOH (1:1 v/v) (10 mL), NaBH4
(0.28 g, 7.38 mmol) added and the mixture stirred at room
temperature for 1 h. The solvent was then evaporated under
reduced pressure and the residue subjected to column chro-
matography on silica, eluting with ether to give 13 (0.78 g,
63%) and 14 (0.11 g, 9%) as colourless thick oils.
5.3.15. 2-(3-Butenyl)-6-[(phenylseleno)methyl]piperidine
18. 5-Oxodeca-1.9-diene oxime O-allyl ether (500 mg,
2.41 mmol) was added to a stirred suspension of phenyl-
selenyl bromide (569 mg, 2.41 mmol) in dry acetonitrile
(20 mL) at room temperature under a nitrogen atmosphere
and stirring was continued for 19 h. Removal of the solvent
under reduced pressure gave the crude salt which was
reduced by addition to a stirred solution of sodiumboro-
hydride (2 equiv.) in 1:1 v/v methanol±chloroform (25 mL)
at room temperature to give a 4:1 mixture of piperidine 18
and pyrrolidine 19. The major product 18 (468 mg, 63%)
was isolated as a colourless thick oil by ¯ash chromato-
graphy eluting with ether. (Found: C, 62.1; H, 7.2; N, 4.3.
C16H23NSe requires: C, 62.35; H, 7.5; N, 4.55%); d 7.50 (m,
2H, ArH), 7.00 (m, 3H, ArH), 5.75 (m, 1H, CHvCH2), 5.00
(m, 2H, CH2vCH), 2.90, 2.80 (2£m, 2H, CH2SePh), 2.60
(m, 1H, Hb), 2.30 (m, 1H, Ha), 2.00 (m, 2H, CH2CHvCH2)
and 1.60±1.00 (m, 9H, 4£CH2 and NH); m/z (%) 308 (M21,
5), 253 (32) and 152 (100).
5.3.11. Compound 13. Found: C, 63.15; H, 8.05; N, 4.3.
C17H25NSe requires: C, 63.35; H, 7.76; N, 4.34%; d 7.50
(m, 2H, ArH), 7.30 (m, 3H, ArH), 5.80 (m, 1H, CHvCH2),
4.98 (m, 2H, CHvCH2), 3.07 (m, 1H, Hc), 2.78 (dd, 1H,
J12.5, 9.5 Hz, Hd), 2.56 (m, 1H, Ha), 2.43 (m, 1H, Hb),
2.15 (m, 3H), 1.78 (m, 1H), 1.65 (m, 1H), 1.56 (m, 1H),
1.50±1.00 (m, 7H); m/z (%) 323(M1, 8), 254 (15), 166 (19),
1
152 (100) and 96 (47). H (NOEDS) irradiation of Ha
caused enhancement of the signal for Hb (1.3%) and
irradiation of Hb caused enhancement of the signal for Ha
(5.6%).
5.3.16. Compound 20. Compound 18 (400 mg, 1.30 mmol)
was added to a stirred solution of mercuric acetate (413 mg,
1.30 mmol) in dry THF (25 mL) and stirring continued at
room temperature for 18 h under a nitrogen atmosphere.
Work up as for 15 afforded the product (72%) as a colour-
less froth. (Found: C, 35.1; H, 4.6; N, 2.4. C18H25NO2SeHg
requires: C, 35.4; H, 4.65; N, 2.6.%); d 7.60±7.20 (m, 5H,
ArH), 3.20 (m, 1H, Hc), 3.35, 3.00 (2£m, 2H, CH2SePh),
2.70 (m, 1H, Hb), 2.40 (m, 1H, Ha), 2.20, 2.05 (2£m, 2H,
CH2HgOAc), 2.00 (s, 3H, Me) and 1.60±1.30 (m, 10H,
5£CH2); m/z (%) 567 (M1, 21), 386 (28) and 283 (100).
5.3.17. 2-(30-Butenyl) cyclohexanone oxime O-allyl ether
21. Prepared from the oxime using allyl bromide. The
product (81%) was obtained as a colourless oil, bp 67±
708C/3 mm Hg. (Found: C, 75.3; H, 10.2; N, 6.7.
C13H21NO requires: C, 75.3; H, 10.2; N, 6.75%); d 6.00
(m, 1H, OCH2CHvCH2), 5.85 (m, 1H, CHvCH2), 5.25
(m, 2H, OCH2CHvCH2), 5.00 (m, 2H, CH2vCH), 4.55
(d, 2H, J5.0 Hz, OCH2), and 2.40±1.30 (m, 13H, 6£CH2
and CH); m/z (%) 207 (M1, 10), 166 (42) and 152 (100).
5.3.12. Compound 14. Found: C, 63.1; H, 7.75; N, 4.4.
C17H25NSe requires: C, 63.35; H, 7.76; N, 4.34%; d 7.50
(d, 2H, J7.5 Hz, ArH), 7.03 (t, 2H, J7.5 Hz, ArH), 6.90
(t, 1H, J7.0 Hz, ArH), 5.70 (m, 1H, CHvCH2), 5.00 (m,
2H, CHvCH2), 3.30 (dd, 1H, J12.5, 5.5 Hz, Hc), 3.13 (m,
1H, Hb), 2.80 (m, 2H, Ha and Hd), 1.90 (q, 2H, J7.0 Hz),
1.70 (m, 1H), 1.46 (m, 3H) and 1.25±1.00 (m, 7H); m/z (%)
1
323 (M1, 2), 254 (12), 166 (9), 152 (100) and 96 (43). H
(NOEDS) irradiation of Ha shows no enhancement of the
signal for Hb and irradiation of Hb shows no enhancement of
the signal for Ha.
5.3.13. Compound 15. Compound 13 (100 mg, 0.30 mmol)
was added to a stirred solution of mercuric acetate (0.095 g,
0.3 mmol) in dry THF (10 mL) and stirring continued at
room temperature for 2 h. The solvent was then removed
under reduced pressure and the residue triturated with ether
to precipitate the product (0.14 g, 78%) which crystallised
from DCM/petroleum ether as colourless prisms, mp 129±
1308C. (Found: C, 38.7; H, 4.75; N, 2.5. C19H27NO2SeHg
requires: C, 39.3; H, 4.5; N, 2.5%); d 7.50 (m, 2H, ArH),
7.24 (m, 3H, ArH), 3.59 (m, 1H, Hc), 3.17 (dd, 1H, J11.5,
6.5 Hz, Hd), 3.00 (dd, 1H, J11.5, 2.0 Hz, He), 2.74 (m, 1H,
Hb), 2.46 (m, 1H, Ha), 2.20 (t, 1H, J11.0 Hz, Hf), 2.06 (m,
1H, Hg), 2.0 (s, 3H, OMe), 1.57 (m, 2H), 1.36 (m, 7H) and
1.26 (m, 3H); m/z (%) 580 (M21, 8), 536(4), 378(90), 324
5.3.18. 2-[(Phenylseleno)methyl]decahydroquinoline 23.
2-(30-Butenyl) oxime O-allyl ether 21 (500 mg, 2.41 mmol)
was added to a stirred suspension of phenylselenyl bromide
(569 mg, 2.41 mmol) in dry acetonitrile (20 mL) at room
temperature under a nitrogen atmosphere and stirring was
continued for 19 h. Removal of the solvent under reduced
pressure gave the crude salt 22 which, without puri®cation,
was reduced by addition to a stirred solution of sodium
borohydride (2 equiv.) in 1:1 v/v methanol±chloroform
(25 mL) at room temperature. Stirring was continued for
19 h. Work up afforded a 4:1 mixture of stereoisomers
was puri®ed by ¯ash chromatography, eluting with ether
1
(100), 244 (80) and 152 (100). H (NOEDS) irradiation of
Ha caused enhancement of the signal for Hb (2.1%) and Hf
(1.2%). Irradiation of Hb caused enhancement of the signal
for Ha (1.8%). Irradiation of Hc caused enhancement of the
proton signals for Hd (4.4%) and He (4.5%).