1454
E. Krawczyk et al. / Tetrahedron 61 (2005) 1449–1457
3
(ethyl acetate/petroleum ether 1:2)Z0.45. Yield: 25%
(20.0 mg from 90.0 mg of 1b); colorless oil; 1H NMR
(CDCl3): dZ0.88 (d, JHHZ7.1 Hz, 3H, CH3CH), 1.28 (t,
3JHHZ7.1 Hz, 3H, OCH2CH3), 1.38 (m, 1H, CH2), 1.68 (bs,
1H, NH), 1.95 (m, 1H, CH2), 2.08 (m, 1H, CH2), 2.11–2.21
(m, 2H, CH2, CH3CH), 3.29 (d, 3JHHZ2.0 Hz, 1H, CHNH),
3
(CDCl3): dZ1.24 (t, JHHZ7.1 Hz, 3H, OCH2CH3), 1.38
3
(d, JHHZ6.5 Hz, 3H, CH3CH), 1.46–2.10 (m, 6H, CH2,
3
2
3
NH), 2.15–2.68 (m, 3H, CH2), 3.85 (q, JHHZ6.5 Hz, 1H,
3.80 (AB, JHHZ12.7 Hz, 2H, CH2NH), 4.19 (q, JHHZ
CH3CH), 3.92 (m, 1H, CHNH), 4.12 (q, 3JHHZ7.1 Hz, 2H,
7.1 Hz, 2H, OCH2), 7.06 (dd, JHHZ3.8, 3.8 Hz, 1H,
CH]C), 7.20–7.38 (m, 5H, CHarom) ppm. 13C NMR
(CDCl3): dZ14.1 (OCH2CH3), 19.2 (CH2), 22.3 (CH3),
28.2 (CH2), 35.1 (CHCH3), 52.3 (NCH2Ph), 54.4 (CHNH),
61.1 (OCH2CH3), 121.9 126.9, 127.2, 128.3 (Carom), 130.2
(C]CH), 138.9 (HC]C), 141.2 (Cipso), 165.5 (C]O). IR
(film, cmK1): 3420 n(NH), 1708 n(C]O). MS (CI,
isobutane): m/z 274 [MCH]C. HRMS (CI) calc. for
C17H23O2NCH [MCH]C 274.1807; found: 274.1814.
3
3
OCH2), 7.12 (dd, JHHZ5.7, 5.7 Hz, 1H, CH]C), 7.23–
7.37 (m, 5H, CHarom) ppm. 13C NMR (CDCl3): dZ14.2
(OCH2CH3), 23.5 (CH3CH), 24.1, 26.0, 27.3, 28.1 (CH2),
52.6, 55.6 (CHN or CHCH3), 60.7 (OCH2CH3), 125.6
(C]CH), 126.6, 127.4, 128.3 (Carom), 144.8 (C]CH),
146.5 (Cipso), 168.0 (C]O). IR (film, cmK1): 3400
n(NH), 1704 n(C]O). MS (CI, isobutane): m/z 288 [MC
H]C. HRMS (CI) calc. for C18H25O2NCH [MCH]C
288.1963; found: 288.1967; [a]2D0ZC4.9 (CHCl3, cZ1.3)
[from S-(K) PhCH(Me)NH2, [a]2D0ZK37.5 (CHCl3, cZ
3.0)].
4.2.13. 6-Benzylamino-3-methyl-cyclohex-1-enecar-
boxylic acid ethyl ester (13). Single diastereoisomer: Rf
(ethyl acetate/petroleum ether 1:2)Z0.49. Yield: 49%
(50.6 mg from 130.0 mg of 1c); colorless oil; 1H NMR
(CDCl3): dZ1.05 (d, 3JHHZ7.3 Hz, 3H, CH3CH), 1.22 (m,
1H, CH2), 1.28 (t, 3JHHZ7.1 Hz, 3H, OCH2CH3), 1.70 (m,
1H, CH2), 1.80 (m, 1H, CH2), 1.87 (bs, 1H, NH), 1.95 (m,
4.2.9. (C)-7-(1-Phenyl-ethylamino)-cyclohept-1-ene-car-
boxylic acid ethyl ester (8b). Single diastereoisomer: Rf
(ethyl acetate/petroleum ether 1:2)Z0.65. Yield: 35%
(18.7 mg from 60.0 mg of 1b); colorless oil; 1H NMR
3
3
(CDCl3): dZ1.23 (t, JHHZ7.1 Hz, 3H, OCH2CH3), 1.41
1H, CH2), 2.40 (m, 1H, CH), 3.61 (dd, JHHZ5.1, 5.1 Hz,
1H, CHNH), 3.79 (AB, JHHZ7.1 Hz, 2H, NHCH2), 4.19
3
3
(d, JHHZ6.5 Hz, 3H, CH3CH), 1.58–1.85 (m, 6H, CH2,
NH), 2.25–2.49 (m, 3H, CH2), 3.84 (m, 1H, CHNH), 3.92
3
3
(q, JHHZ7.1 Hz, 2H, OCH2), 6.92 (d, JHHZ5.0 Hz, 1H,
CH]C), 7.20–7.36 (m, 5H, CHarom) ppm. 13C NMR
(CDCl3): 14.5 (OCH2CH3), 19.7 (CH2), 20.5 (CH3), 24.7
(CH2), 30.0 (CHCH3), 52.0 (NCH2Ph), 55.4 (CHNH), 60.1
(OCH2CH3), 126.1 (C]CH), 126.9, 127.1, 128.0 (Carom),
141.70 (Cipso), 142.2 (HC]C), 165.5 (C]O). IR (film,
cmK1): 3400 n(NH), 1705 n(C]O). MS (CI, isobutane):
m/z 274 [MCH]C. HRMS (CI) calc. for C17H24O2NCH
[MCH]C 274.1807; found: 274.1810.
(q, 3JHHZ6.3 Hz, 1H, CH3CH), 4.12 (q, 3JHHZ7.1 Hz, 1H,
3
OCH2), 4.14 (q, JHHZ7.1 Hz, 1H, OCH2), 7.16–7.37 (m,
6H, CH]C, CHarom) ppm. [a]2D0ZC33.5 (CHCl3, cZ0.2)
[from R-(C) PhCH(Me)NH2, [a]2D0ZC27.4 (MeOH, cZ
2.4)]. IR and MS spectra were identical to those of the
isomer 8a.
4.2.10. (K)-7-(1-Phenyl-ethylamino)-cyclohept-1-ene-
carboxylic acid ethyl ester (8b0). Single diastereoisomer:
Rf (ethyl acetate/petroleum ether 1:2)Z0.45. Yield: 25%
(13.0 mg from 60.0 mg of 1b); colorless oil; 1H NMR
4.2.14. 6-Azido-5-methyl-cyclohex-1-enecarboxylic acid
ethyl ester (14) and 6-Azido-3-methyl-cyclohex-1-ene-
carboxylic acid ethyl ester (15). Ratio of regioisomers:
2:1: Rf (ethyl acetate/petroleum ether 1:2)Z0.73 and 0.66.
Yield: 70% (41.0 mg from 95.0 mg of 1c); colorless oil; 1H
3
(CDCl3): dZ1.25 (t, JHHZ7.2 Hz, 3H, OCH2CH3), 1.40
3
(d, JHHZ6.4 Hz, 3H, CH3CH), 1.57–2.04 (m, 6H, CH2,
NH), 2.23–2.53 (m, 3H, CH2), 3.85–3.90 (four lines, 3JHH
Z
3
3
2.1, 6.3 Hz, 2H, CH3CH, CHNH), 4.12 (q, JHHZ7.2 Hz,
NMR (CDCl3): dZ0.97 (d, JHHZ7.7 Hz, 3H, CH3CH,
3
major), 1.05 (d, 3JHHZ7.3 Hz, 3H, CH3CH, minor), 1.32 (t,
3JHHZ7.1 Hz, 6H, OCH2CH3), 1.34–1.50 (m, 2H, CH2),
1.55–2.08 (m, 5H, CH2), 2.15–2.35 (m, 2H, CH2, CH), 2.41
1H, OCH2), 4.13 (q, JHHZ7.1 Hz, 1H, OCH2), 7.11–7.23
(m, 1H, CH]C), 7.28–7.35 (m, 5H, CHarom) ppm.
[a]2D0ZK6.8
(CHCl3,
cZ0.25)
[from
R-(C)
PhCH(Me)NH2, [a]2D0ZC27.4 (MeOH, cZ2.4)]. IR and
MS spectra were identical to those of the isomer 8a0.
3
(m, 1H, CH), 4.05 (d, JHHZ3.8 Hz, 1H, CHN3, major),
4.25 (m, 4H, OCH2), 4.38 (m, 1H, CHN3, minor), 7.07 (d,
3JHHZ4.1 Hz, CH]C, 1H, minor), 7.19 (dd, JHHZ3.9,
3
4.2.11. 6-Azido-cyclohex-1-enecarboxylic acid ethyl ester
(9). Rf (ethyl acetate/petroleum ether 1:1)Z0.74. Yield:
65% (40.0 mg from 97.0 mg of 1a); colorless oil; 1H NMR
3.9 Hz, 1H, CH]C, major) ppm. 13C NMR (CDCl3): dZ
13.6, 14.1 (OCH2CH3), 14.8 (CH3, major), 20.9, 22.4, 24.3,
25.1 (CH2, major and minor), 30.6, 35.1 (CHCH3, major and
minor), 54.2 (CHN3, minor), 57.8 (CHN3, major), 61.7
(OCH2CH3, major), 63.1 (OCH2CH3, minor), 131.5
(C]CH, minor), 133.0 (C]CH, major), 140.3 (HC]C,
major), 143.2 (HC]C, minor), 167.8 (C]O, major and
minor). IR (film, cmK1): 2112, 2110 n(N3), 1710 n(C]O).
MS (CI, isobutane): m/z 210 [MCH]C. HRMS (CI) calc.
for C10H15O2N3CH [MCH]C 210.1242; found: 210.1247.
3
(CDCl3): dZ1.32 (t, JHHZ7.1 Hz, 3H, OCH2CH3), 1.50–
1.80 (m, 4H, CH2), 1.90–2.42 (m, 2H, CH2), 4.25 (q, 3JHH
7.1 Hz, 2H, OCH2), 4.45 (m, 1H, CHN3), 7.23 (dd, 3JHH
Z
Z
2.4, 2.4 Hz, 1H, CH]C) ppm. 13C NMR (CDCl3): dZ14.3
(OCH2CH3), 22.8, 24.1, 26.2 (CH2), 55.2 (CHN3), 60.9
(OCH2CH3), 131.8 (C]CH), 140.3 (HC]C), 167.8
(C]O). IR (film, cmK1): 2100 n(N3), 1706 n(C]O). MS
(CI, isobutane): m/z 196 [MCH]C. HRMS (CI) calc. for
C9H13O2N3CH [MCH]C 196.1086; found: 196.1081.
4.2.15. 6-Diethylamino-3-methyl-cyclohex-1-enecar-
boxylic acid ethyl ester (16). Rf (ethyl acetate/petroleum
ether 1:2)Z0.78. Yield: 78% (75.0 mg from 128.0 mg of
4.2.12. 6-Benzylamino-5-methyl-cyclohex-1-enecar-
boxylic acid ethyl ester (12). Single diastereoisomer: Rf
(ethyl acetate/petroleum ether 1:2)Z0.71. Yield: 31%
(31.0 mg from 130.0 mg of 1c); colorless oil; 1H NMR
1
3
1c); colorless oil; H NMR (CDCl3): dZ0.97 (t, JHH
Z
3
7.0 Hz, 6H, NCH2CH3), 0.99 (d, JHHZ7.1 Hz, 3H,
CH3CH), 1.28 (t, JHHZ7.1 Hz, 3H, OCH2CH3), 1.52 (m,
3