A. Kakuuchi et al. / Tetrahedron 60 (2004) 1293–1299
1297
CDCl3) d 29.6, 32.8, 41.2, 44.9, 51.3, 126.3, 126.4, 126.7,
127.3, 128.5, 142.2, 143.5, 172.3; ESI m/z 269 [MþNa]þ;
HRMS Calcd for C16H22O2Na: 269.1517. Found: 269.1518;
Anal. Calcd for C16H22O2: C, 78.01; H, 9.09; O, 12.99.
Found: C, 77.99; H, 9.02.
4.2.14. 3-[(E)-3,6,6-Trimethyl-4-heptenoyl]-1,3-oxazoli-
din-2-one (7c). Mp 33–34 8C; IR (neat) 1770,
n
1698 cm21; H NMR (400 MHz, CDCl3) d 0.94 (s, 9H),
1.04 (d, J¼6.7 Hz, 3H), 2.65 (sep, J¼7.0 Hz, 1H), 2.82 (dd,
J¼6.9, 15.3 Hz, 1H), 2.98 (dd, J¼7.5, 15.3 Hz, 1H), 3.96 (t,
J¼8.1 Hz, 2H), 4.35 (t, J¼8.1 Hz, 2H), 5.24 (dd, J¼7.7,
15.6 Hz, 1H), 5.43 (d, J¼15.6 Hz, 1H); 13C NMR
(75.5 MHz, CDCl3) d 20.6, 29.6, 32.5, 33.6, 42.0, 42.4,
61.8, 128.5, 140.6, 153.4, 172.4; ESI m/z 262 [MþNa]þ;
HRMS Calcd for C13H21O3NNa: 262.1419. Found:
262.1433.
1
4.2.9. iso-Propyl (E)-6,6-dimethyl-3-phenyl-4-hepteno-
ate (6b). IR (neat) n 1733 cm21 1H NMR (400 MHz,
;
CDCl3) d 0.99 (s, 9H), 1.14 (d, J¼6.3 Hz, 3H), 1.18 (d,
J¼6.3 Hz, 3H), 2.65 (d, J¼7.8 Hz, 2H), 3.79 (q,
J¼7.6 Hz, 1H), 4.93 (sep, J¼6.3 Hz, 1H), 5.45–5.51
(dd, J¼7.0, 15.7 Hz, 1H), 5.56 (d, J¼15.7 Hz, 1H), 7.18–
7.32 (m, 5H); 13C NMR (75.5 MHz, CDCl3) d 21.7, 21.8,
29.6, 32.8, 41.6, 44.9, 67.5, 126.3, 126.5, 127.4, 128.4,
141.9, 143.6, 171.5; ESI m/z 297 [MþNa]þ; HRMS
Calcd for C18H26O2Na: 297.1831. Found: 297.1815;
Anal. Calcd for C18H26O2: C, 78.77; H, 9.56; O, 11.66.
Found: C, 78.77; H, 9.56.
4.2.15. 3-[(E)-3-Methyl-4-nonenoyl]-1,3-oxazolidin-2-
one (7d). IR (neat) n 1781, 1700 cm21
;
1H NMR
(400 MHz, CDCl3) d 0.82 (t, J¼7.1 Hz, 3H), 1.02 (d,
J¼6.8 Hz, 3H), 1.22–1.30 (m, 4H), 1.90–1.95 (m, 2H),
2.67 (sep, J¼6.8 Hz, 1H), 2.80 (dd, J¼6.8, 15.7 Hz, 1H),
2.96 (dd, J¼8.1, 15.7 Hz, 1H), 3.96 (t, J¼8.1 Hz, 2H), 4.07
(t, J¼8.1 Hz, 2H), 5.30–5.43 (m, 2H); 13C NMR
(75.5 MHz, CDCl3) d 13.8, 20.5, 22.0, 31.5, 32.0, 33.1,
41.9, 42.4, 61.8, 129.5, 133.9, 153.3, 172.2; ESI m/z 262
[MþNa]þ; HRMS Calcd for C13H21O3NNa: 262.1419.
Found: 262.1424.
4.2.10. tert-Butyl (E)-6,6-dimethyl-3-phenyl-4-hepteno-
ate (6c). IR (neat) n 1733 cm21 1H NMR (400 MHz,
;
CDCl3) d 1.00 (s, 9H), 1.37 (s, 9H), 2.60 (d, J¼7.8 Hz, 2H),
3.77 (q, J¼7.6 Hz, 1H), 5.45–5.51 (dd, J¼6.9, 15.7 Hz,
1H), 5.57 (d, J¼15.7 Hz, 1H), 7.18–7.31 (m, 5H); 13C
NMR (75.5 MHz, CDCl3) d 28.0, 29.6, 32.8, 42.3, 44.9,
80.1, 126.2, 126.7, 127.4, 128.3, 141.7, 143.8, 171.2; ESI m/
z 311 [MþNa]þ; HRMS Calcd for C19H28O2Na: 311.1987.
Found: 311.1988; Anal. Calcd for C19H28O2: C, 79.12; H,
9.78; O, 11.09. Found: C, 79.08; H, 9.75.
4.2.16. (4R)-4-Phenyl-3-[(3,4E)-3,6,6-trimethyl-4-hepte-
noyl]-1,3-oxazolidine-2-one (minor-11a). Less polar iso-
mer, oil; [a]2D5¼273.8 (c 0.86, CHCl3); IR (neat) n 1778,
1
1702 cm21; H NMR (400 MHz, CDCl3) d 0.91 (s, 9H),
0.98 (d, J¼6.7 Hz, 3H), 2.64 (sep, J¼6.9 Hz, 1H), 2.88 (dd,
J¼6.4, 15.4 Hz, 1H), 2.96 (dd, J¼7.8, 15.4 Hz, 1H), 4.25
(dd, J¼3.7, 8.9 Hz, 1H), 4.65 (t, J¼8.8 Hz, 1H), 5.20 (dd,
J¼7.6, 15.6 Hz, 1H), 5.37 (dd, J¼0.7, 15.3 Hz, 1H), 5.41
(dd, J¼3.7, 8.8 Hz, 1H), 7.28–7.39 (m, 5H); 13C NMR
(75.5 MHz, CDCl3) d 20.7, 29.6, 32.5, 33.5, 42.5, 57.5,
69.8, 125.9, 128.4, 128.6, 129.1, 139.2, 140.7, 153.7, 171.6;
ESI m/z 338 [MþNa]þ; HRMS Calcd for C19H25O3NNa:
338.1732. Found: 338.1703.
4.2.11. Methyl 3-[(E)-3,3-dimethyl-1-butene-1-yl]octano-
ate (6d). IR (neat) n 1743 cm21 1H NMR (400 MHz,
;
CDCl3) d 0.84 (t, J¼6.7 Hz, 3H), 0.96 (s, 9H), 1.21–1.34
(m, 8H), 2.21 (dd, J¼8.6, 14.0 Hz, 1H), 2.33 (dd, J¼6.0,
14.0 Hz, 1H), 2.38–2.42 (m, 1H), 3.62 (s, 3H), 5.06 (dd,
J¼8.6, 15.6 Hz, 1H), 5.44 (d, J¼15.6 Hz, 1H); 13C NMR
(75.5 MHz, CDCl3) d 14.0, 22.5, 26.6, 29.7, 31.6, 32.7,
34.9, 39.7, 40.9, 51.2, 126.9, 142.4, 173.2; ESI m/z 263
[MþNa]þ; HRMS Calcd for C15H28O2Na: 263.1987.
Found: 263.1980.
4.2.17. (4R)-4-Phenyl-3-[(3,4E)-3,6,6-trimethyl-4-hepte-
noyl]-1,3-oxazolidine-2-one (major-11a). More polar iso-
mer, crystals, mp 46–47 8C; [a]2D5¼2114.33 (c 0.22,
CHCl3); IR (neat) n ;
1778, 1702 cm21 1H NMR
4.2.12. (E)-N-Benzyl-3,6,6-trimethyl-4-heptenamide
(7a). Crystals, mp 56–58 8C; IR (neat)
n
3270,
(400 MHz, CDCl3) d 0.91 (s, 9H), 0.97 (d, J¼6.8 Hz, 3H),
2.66 (sep, J¼6.8 Hz, 1H), 2.85 (dd, J¼7.5, 16.2 Hz, 1H), 3.0
(dd, J¼6.6, 16.2 Hz, 1H), 4.27 (dd, J¼3.7, 8.9 Hz, 1H), 4.67
(t, J¼8.9 Hz, 1H), 5.21 (dd, J¼7.2, 15.7 Hz, 1H), 5.40 (dd,
J¼1.0, 15.7 Hz, 1H), 5.42 (dd, J¼3.7, 8.7 Hz, 1H), 7.27–
7.38 (m, 5H); 13C NMR (75.5 MHz, CDCl3) d 20.4, 29.6,
32.5, 32.6, 42.6, 57.6, 69.8, 125.9, 128.6, 128.7, 129.1,
139.1, 140,153.7,171.6; ESI m/z338 [MþNa]þ; HRMS
Calcd for C19H25O3NNa: 338.32. Found: 338.1714.
1641 cm21; H NMR (300 MHz, CDCl3) d 0.94 (s, 9H),
0.98 (d, J¼6.8 Hz, 3H), 2.14 (dd, J¼6.9, 14.1 Hz, 1H), 2.20
(dd, J¼7.5, 14.0 Hz, 1H), 2.62 (sep, J¼6.9 Hz, 1H), 4.39
(m, 2H), 5.22 (dd, J¼7.4, 15.7 Hz, 1H), 5.47 (d, J¼15.6 Hz,
1H), 6.05 (bs, 1H), 7.24–7.32 (m, 5H); 13C NMR
(75.5 MHz, CDCl3) d 20.7, 29.6, 32.5, 33.9, 43.4, 44.4,
127.3, 127.7, 128.5, 128.8, 138.3, 140.8, 171.8; ESI m/z 282
[MþNa]þ; HRMS Calcd for C17H25NONa: 282.1834;
Found: 282.1811.
1
4.2.18. (4S)-4-iso-Propyl-3-[(3p,4E)-3,6,6-trimethyl-4-
heptenoyl]-1,3-oxazolidine-2-one (minor-11b). Less
polar isomer, oil; [a]D25¼þ73.3 (c 1.12, CHCl3); IR (neat)
n 1783, 1701 cm21; 1H NMR (400 MHz, CDCl3) d 0.86 (d,
J¼6.9 Hz, 3H), 0.90 (d, J¼7.0 Hz, 3H), 0.95 (s, 9H), 1.06
(d, J¼6.7 Hz, 3H), 2.29–2.36 (m, 1H), 2.68 (sep, J¼7.0 Hz,
1H), 2.84 (dd, J¼8.0, 14.8 Hz, 1H), 2.97 (dd, J¼6.3,
14.9 Hz, 1H), 4.18 (dd, J¼3.3, 9.1 Hz, 1H), 4.22 (t,
J¼8.6 Hz, 1H), 4.41 (dt, J¼3.5, 8.2 Hz, 1H), 5.24 (dd,
J¼7.8, 15.6, 1 Hz), 5.44 (dd, 1H, J¼0.6, 15.7 Hz); 13C
NMR (75.5 MHz, CDCl3) d 14.6, 17.9, 21.0, 28.4, 29.7,
4.2.13. (E)-3,6,6-Trimethyl-1-(1-piperidinyl)-4-hepten-1-
one (7b). IR (neat) n 1642 cm21 1H NMR (400 MHz,
;
CDCl3) d 0.95 (s, 9H), 1.01 (d, J¼6.7 Hz, 3H), 1.49–1.64
(m, 6H), 2.20 (dd, J¼7.9, 14.2 Hz, 1H), 2.33 (dd, J¼6.6,
14.2 Hz, 1H), 2.61 (sep, J¼6.9 Hz, 1H), 3.37–3.56 (m, 4H),
5.24 (dd, J¼7.3, 15.6 Hz, 1H), 5.43 (d, J¼15.6 Hz, 1H); 13C
NMR (75.5 MHz, CDCl3) d 20.5, 24.5, 25.6, 26.6, 29.7,
32.5, 33.9, 40.6, 42.6, 47.0, 129.1, 140.0, 170.0; ESI m/z 260
[MþNa]þ; HRMS Calcd for C15H27ONNa: 260.1990.
Found: 260.2011.