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T. Takanami et al. / Tetrahedron 62 (2006) 9467–9474
1Hꢁ0.31, PhCH in (Z)-2b), 3.82 (q, J¼7.2 Hz, 1Hꢁ0.69,
PhCH in (E)-2b), 2.81–2.78 (m, 2H), 2.07 (s, 3Hꢁ0.31,
COCH3 in (Z)-2b), 2.06 (s, 3Hꢁ0.69, COCH3 in (E)-2b),
1.68 (d, J¼5.1 Hz, 3Hꢁ0.31, CH]CHCH3 in (Z)-2b),
4.4.6. (E)-3-Methyl-5-phenylpent-4-enal (4a). Colorless
1
oil; H NMR (CDCl3, 300 MHz) d 9.76 (t, J¼2.2 Hz, 1H,
CHO), 7.34–7.17 (m, 5H), 6.40 (d, J¼15.9 Hz, 1H, CH]
CH–Ph), 6.14 (dd, J¼15.9 and 7.3 Hz, 1H, CH]CH–Ph),
2.99–2.89 (m, 1H, MeCH), 2.59–2.38 (m, 2H), 1.16 (d,
J¼6.8 Hz, 3H, CH3); 13C NMR (CDCl3, 67.8 MHz)
d 202.1, 137.1, 133.9, 129.1, 128.5, 127.3, 126.1, 50.4,
31.9, 20.4; IR (neat) 694, 750, 969, 1073, 1450, 1493,
1601, 1725, 2968 cmꢂ1. Exact EIMS calcd for C12H14O:
174.1045. Found: 174.1048.
1.63 (d, J¼6.2 Hz, 3Hꢁ0.69, CH]CHCH3 in (E)-2b); 13
C
NMR (CDCl3, 100 MHz) for (E)-2b: d 207.0, 143.6,
133.3, 128.4, 127.3, 126.3, 125.3, 49.8, 44.0, 30.7, 18.0;
13C NMR (CDCl3, 100 MHz) for (Z)-2b: d 206.5, 143.6,
132.6, 128.5, 127.0, 126.2, 124.7, 50.5, 44.1, 31.2, 14.3;
IR (neat) 2920, 1717, 1603, 1493, 1454, 1359, 1162, 969,
754, 733, 540 cmꢂ1. Exact EIMS calcd for C13H16O:
188.1201. Found: 188.1199.
4.4.7. 3-Propenylheptanal (4c) (E/Z¼28:72).5d,12 Color-
1
less oil; H NMR (300 MHz, CDCl3) d 9.67 (t, J¼2.4 Hz,
4.4.3. 1,3-Diphenylhex-4-en-1-one (2c) (E/Z¼76:24). Col-
orless oil; 1H NMR (CDCl3, 300 MHz) d 7.93–7.89 (m, 2H),
7.56–7.40 (m, 3H), 7.30–7.14 (m, 5H), 5.68–5.38 (m, 2H,
CH]CH), 4.40 (dt, J¼8.3 and 6.3 Hz, 1Hꢁ0.24, PhCH in
(Z)-2c), 4.05 (dt, J¼7.0 and 7.0 Hz, 1Hꢁ0.76, PhCH in
(E)-2c), 3.42–3.25 (m, 2H), 1.65 (dd, J¼6.3 and 1.4 Hz,
3Hꢁ0.24, m, CH3 in (Z)-2c), 1.62 (ddd, J¼6.3, 1.5, and
1.1 Hz, 3Hꢁ0.76, CH3 in (E)-2c); 13C NMR (CDCl3,
100 MHz) for (E)-2c: d 198.2, 143.9, 137.1, 133.4, 132.8,
128.4, 128.0, 127.9, 127.4, 126.2, 125.4, 44.8, 43.9, 18.1;
13C NMR (CDCl3, 100 MHz) for (Z)-2c: d 197.7, 144.3,
137.1, 133.4, 132.7, 128.5, 128.4, 127.9, 127.1, 126.1,
124.8, 45.7, 38.9, 13.3; IR (neat) 2920, 1688, 1601, 1582,
1493, 1452, 971 cmꢂ1. Exact EIMS calcd for C18H18O:
250.1358. Found: 250.1361. Anal. calcd for C18H18O: C,
86.36; H, 7.25; O, 6.39. Found: C, 86.47; H, 7.33.
1Hꢁ0.28, CHO in (E)-4c), 9.66 (t, J¼2.4 Hz, 1Hꢁ0.72,
CHO in (Z)-4c), 5.49 (ddq, J¼10.4, 6.8, and 0.9 Hz,
1Hꢁ0.72, CH]CH–Me in (Z)-4c), 5.45 (ddq, J¼15.2,
5.9, and 0.7 Hz, 1Hꢁ0.28, CH]CH–Me in (E)-4c), 5.24
(ddq, J¼15.2, 8.3, and 1.5 Hz, 1Hꢁ0.28, CH]CH–Me in
(E)-4c), 5.13 (ddq, J¼10.4, 10.4, and 1.8 Hz, 1Hꢁ0.72,
CH]CH–Me in (Z)-4c), 2.97–2.84 (m, 1Hꢁ0.72, BuCH
in (Z)-4c), 2.58–2.48 (m, 1Hꢁ0.28, BuCH in (E)-4c),
2.44–2.23 (m, 2H), 1.63 (dd, J¼5.9 and 1.7 Hz, 3Hꢁ0.32,
CH]CH–CH3 in (E)-4c), 1.62 (dd, J¼6.8 and 1.6 Hz,
3Hꢁ0.72, CH]CH–CH3 in (Z)-4c), 1.36–1.14 (m, 6H),
0.86 (t, J¼6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz) for
(E)-4c: d 202.7, 133.6, 125.7, 49.2, 37.6, 35.1, 29.3, 22.7,
18.0, 14.2; 13C NMR (CDCl3, 100 MHz) for (Z)-4c:
d 202.4, 133.2, 124.7, 49.7, 37.6, 35.4, 29.4, 22.8, 18.0,
14.2; IR (neat) 1729, 1460, 1408, 1379, 1263, 1067, 969,
932, 803, 729 cmꢂ1. Exact EIMS calcd for C10H18O:
154.1358. Found: 154.1353.
4.4.4. 3-(4-Methoxyphenyl)hex-4-enal (2f) (E/Z¼38:62).
Colorless oil; 1H NMR (CDCl3, 300 MHz) d 9.68 (t,
J¼2.2 Hz, 1Hꢁ0.62, CHO in (Z)-2f), 9.67 (t, J¼2.2 Hz,
1Hꢁ0.38, CHO in (E)-2f), 7.13 (d, J¼8.7 Hz, 2H), 6.83
(d, J¼8.7 Hz, 2H), 5.58–5.46 (m, 2H, CH]CH), 4.18 (q,
J¼6.8 Hz, 1Hꢁ0.62, ArCH in (Z)-2f), 3.83 (q, J¼7.1 Hz,
1Hꢁ0.38, ArCH in (E)-2f), 3.76 (s, 3H, OCH3), 2.82–2.64
(m, 2H), 1.69 (d, J¼5.1 Hz, 3Hꢁ0.62, CH]CHCH3 in
(Z)-2f), 1.64 (d, J¼5.9 Hz, 3Hꢁ0.38, CH]CHCH3 in (E)-
2f); 13C NMR (CDCl3, 67.8 MHz) for (E)-2f: d 201.9,
158.3, 135.1, 133.3, 128.3, 125.7, 114.1, 55.3, 49.3, 42.0,
17.9; 13C NMR (CDCl3, 67.8 MHz) for (Z)-2f: d 201.7,
158.2, 135.5, 132.6, 128.0, 124.7, 114.0, 55.2, 50.2, 36.5,
13.1; IR (neat) 3828, 2840, 1725, 1611, 1584, 1514, 1251,
1180, 1036, 971, 830 cmꢂ1. Exact EIMS calcd for
C13H16O2: 204.1150. Found: 204.1149.
4.4.8. 4-Propenyloctan-2-one (4d) (E/Z¼77:23). Colorless
oil; 1H NMR (CDCl3, 300 MHz) d 5.51–5.34 (m, 1H,
CH]CH–Me), 5.19 (ddq, J¼15.2, 8.3, and 1.6 Hz,
1Hꢁ0.77, CH]CH–Me in (E)-4d), 5.08 (ddq, J¼9.9, 9.9,
and 1.8 Hz, 1Hꢁ0.23, CH]CH–Me in (Z)-4d), 2.93–2.80
(m, 1Hꢁ0.23, BuCH in (Z)-4d), 2.50–2.43 (m, 1Hꢁ0.77,
BuCH in (E)-4d), 2.42–2.26 (m, 2H), 2.09 (s, 3Hꢁ0.23,
COCH3 in (Z)-4d), 2.08 (s, 3Hꢁ0.77, COCH3 in (E)-4d),
1.61 (dd, J¼6.2 and 1.6 Hz, 3Hꢁ0.77, CH]CH–CH3 in
(E)-4d), 1.61 (dd, J¼7.0 and 1.5 Hz, 3Hꢁ0.23, CH]CH–
CH3 in (Z)-4d), 1.31–1.18 (m, 6H), 0.86 (t, J¼6.4 Hz,
3H); 13C NMR (CDCl3, 100 MHz) for (E)-4d: d 208.3,
133.9, 125.2, 49.9, 38.8, 35.1, 30.6, 29.4, 22.8, 18.0, 14.2;
13C NMR (CDCl3, 100 MHz) for (Z)-4d: d 208.2, 133.7,
124.4, 50.2, 38.8, 35.4, 30.7, 29.5, 22.9, 18.0, 13.3; IR
(neat) 729, 969, 1166, 1359, 1458, 1717, 2930 cmꢂ1. Exact
EIMS calcd for C11H20O: 168.1514. Found: 168.1514.
4.4.5. 3-(p-Tolyl)hex-4-enal (2g) (E/Z¼39:61). Colorless
oil; 1H NMR (CDCl3, 300 MHz) d 9.68 (t, J¼2.2 Hz,
1Hꢁ0.61, CHO in (Z)-2g), 9.68 (t, J¼2.2 Hz, 1Hꢁ0.39,
CHO in (E)-2g), 7.16–7.04 (m, 4H), 5.58–5.47 (m, 2H,
CH]CH), 4.19 (q, J¼6.6 Hz, 1Hꢁ0.61, ArCH in (Z)-2g),
3.84 (q, J¼7.3 Hz, 1Hꢁ0.39, ArCH in (E)-2g), 2.84–2.66
(m, 2H), 2.30 (s, 3H, ArCH3), 1.69 (d, J¼5.1 Hz,
3Hꢁ0.61, CH]CHCH3 in (Z)-2g), 1.64 (d, J¼5.9 Hz,
3Hꢁ0.39, CH]CHCH3 in (E)-2g); 13C NMR (CDCl3,
67.8 MHz) for (E)-2g: d 201.9, 140.0, 136.2, 133.2, 129.4,
127.2, 125.8, 49.2, 42.4, 21.0, 17.9; 13C NMR (CDCl3,
67.8 MHz) for (Z)-2g: d 201.7, 158.6, 135.9, 128.3, 128.0,
124.7, 114.1, 55.2, 50.2, 36.5, 13.1; IR (neat) 2924, 2728,
1721, 1516, 1452, 1417, 1381, 1112, 1044, 1021, 969,
816 cmꢂ1. Exact EIMS calcd for C13H16O: 188.1201.
Found: 188.1202.
4.4.9. 1-Phenyl-3-propenylheptan-1-one (4e) (E/Z¼
1
80:20). Colorless oil; H NMR (CDCl3, 300 MHz) d 7.92–
7.89 (m, 2H), 7.55–7.40 (m, 3H), 5.48–5.34 (m, 1H,
CH]CH–Me), 5.26 (ddq, J¼15.1, 7.9, and 1.5 Hz,
1Hꢁ0.8, CH]CH–Me in (E)-4e), 5.14 (ddq, J¼10.8,
10.8, and 1.8 Hz, 1Hꢁ0.2, CH]CH–Me in (Z)-4e), 3.11–
3.00 (m, 1Hꢁ0.2, BuCH in (Z)-4e), 2.91 (d, J¼7.4 Hz,
2H, PhCOCH2), 2.70–2.59 (m, 1Hꢁ0.8, BuCH in (E)-4e),
1.59 (dd, J¼6.2 and 1.3 Hz, 3Hꢁ0.8, CH]CH–CH3 in
(E)-4e), 1.54 (dd, J¼6.8 and 1.8 Hz, 3Hꢁ0.2, CH]CH–
CH3 in (E)-4e), 1.45–1.17 (m, 6H), 0.86 (t, J¼6.8 Hz, 3H);
13C NMR (CDCl3, 100 MHz) for (E)-4e: d 199.6, 137.4,
134.2, 132.6, 128.3, 128.0, 125.1, 44.7, 39.0, 35.0, 29.5,