M. Fujii et al. / Tetrahedron: Asymmetry 17 (2006) 2292–2298
2297
H-1a), 5.24 (1H, dt, J = 1.2, 17.3 Hz, H-1b), 5.42 (1H, br q,
4.7. (3S)-Non-1-en-3-yl crotonate (S)-13
J = 6.8 Hz, H-3), 5.70 (1H, ddd, J = 6.8, 10.5, 17.3 Hz, H-
2), 7.35–7.40 (3H, m, Ph), 7.49–7.51 (2H, m, Ph).
From rac-10 (501 mg, 3.52 mmol) to (S)-13 (347 mg,
1.62 mmol, 94% yield based on 50% conv., >99% ee). Col-
4.4. (3R)-Hept-1-en-3-yl acrylate (R)-5
orless oil. GC column temp.: 110 °C, tR: 26.8 min for (R)-
26
13 and 27.8 min for (S)-13. ½aꢁD ¼ ꢀ7:0 (c 1.01, CHCl3). 1H
To (R)-4 (5.7 g, 50 mmol) in dichloromethane (200 mL)
containing triethylamine (5.6 g, 51 mmol) was added acyl-
oyl chloride (4.6 g, 51 mmol) at 0 °C and the mixture was
stirred for 1 h at 0 °C. The mixture was added to water
(15 mL) and the organic layer was removed. The organic
layer was dried over sodium sulfate, concentrated under re-
duced pressure. The residue was purified by bulb-to-bulb
distillation (0.2 mmHg, 70 °C) to afford (R)-5 (7.2 g,
43 mmol, 86%).
NMR (400 MHz, CDCl3): d 0.85 (3H, t, J = 6.6 Hz), 1.24–
1.33 (8H, m), 1.52–1.66 (2H, m), 1.86 (3H, dd, J = 1.7,
7.1 Hz), 5.13 (1H, td, J = 1.2, 10.5 Hz), 5.21 (1H, td,
J = 1.2, 17.3 Hz), 5.26 (1H, tq, J = 1.2, 6.1 Hz), 5.78 (1H,
ddd, J = 6.1, 10.5, 17.3 Hz), 5.84 (1H, qd, J = 1.7,
15.6 Hz), 6.97 (1H, qd, J = 7.1, 15.6 Hz). 13C NMR
(100 MHz, CDCl3): d 14.0, 17.9, 22.6, 25.0, 29.0 31.7,
34.3, 74.5, 116.2, 123.0, 136.7, 144.5, 165.9. HR-FAB-MS
m/z: 211.1698 ([M+H]+, calcd for C13H23O2 m/z:
211.1698). IR (neat) m: 3087, 3054, 3013, 2955, 2930,
4.5. (3S)-Hex-1-en-3-yl crotonate (S)-11
2860, 1722, 1658, 1181 cmꢀ1
.
From rac-8 (500 mg, 5.00 mmol) to (S)-11 (335 mg,
4.8. Typical procedure for RCM (Table 3, entry 5)
1.99 mmol, 80% based on 50% conv., 98% ee). Colorless
oil. GC column temp.: 85 °C, tR: 15.8 min for (R)-11 and
To a refluxed solution of (S)-hept-1-en-3-yl crotonate (S)-7
(115 mg 0.632 mmol) in dichloromethane (100 mL) was
dropwise added Grubbs’ catalyst II (50 mg, 0.06 mmol) in
dichloromethane (20 mL) for 1 h, and refluxed for 1 day
under a nitrogen atmosphere. The reaction mixture was
then concentrated under reduced pressure. The residue
was subjected to silica gel column chromatography (silica
gel: 10 g, hexane–acetone = 15/1) to afford (S)-oct-2-en-4-
olide (S)-1 (85.4 mg, 0.610 mmol, 96%).
26
17.5 min for (S)-11. ½aꢁD ¼ þ6:9 (c 1.00, CHCl3). 1H
NMR (400 MHz, CDCl3): d 0.90 (3H, t, J = 6.8 Hz),
1.28–1.40 (2H, m), 1.51–1.68 (2H, m), 1.86 (3H, dd,
J = 1.5, 6.8 Hz), 5.12 (1H, td, J = 1.2, 10.5 Hz), 5.21 (1H,
td, J = 1.2, 17.3 Hz), 5.28 (1H, tq, J = 1.2, 6.4 Hz), 5.78
(1H, ddd, J = 6.4, 10.5, 17.3 Hz), 5.84 (1H, qd, J =
1.5, 15.6 Hz), 6.96 (1H, qd, J = 6.8, 15.6 Hz). 13C NMR
(100 MHz, CDCl3): d 13.5, 17.6, 18.0, 36.0, 73.8, 115.8,
122.6, 136.4, 144.1, 165.5. HR-FAB-MS m/z: 169.1247
([M+H]+, calcd for C10H17O2 m/z: 169.1229). IR (neat) m:
4.9. (S)-Oct-2-en-4-olide (S)-1
3087, 3054, 3014, 2961, 2937, 2874, 1721, 1658, 1182 cmꢀ1
.
22
Colorless oil. ½aꢁD ¼ þ100:4 (c 1.01, CHCl3), lit.2a +100.8
(3R)-Hex-1-en-3-yl (R)-(+)-2-methoxy-2-trifluoromethyl-2-
phenylacetate [(R)-8-(R)-MTPA ester]. 1H NMR
(400 MHz, CDCl3): d 0.82 (3H, t, J = 7.3 Hz, H-6), 1.15–
1.28 (2H, m, H-5), 1.54–1.69 (2H, m, H-4), 3.59 (3H, q,
J = 1.5 Hz, OCH3), 5.22 (1H, td, J = 1.2, 10.5 Hz, H-1a),
5.32 (1H, dd, J = 1.2, 17.1 Hz, H-1b), 5.43 (1H, tq,
J = 1.2, 6.3 Hz, H-3), 5.78 (1H, ddd, J = 6.4, 10.5,
17.1 Hz, H-2), 7.34–7.39 (3H, m, Ph), 7.50–7.53 (2H, m,
Ph). For [(S)-8-(R)-MTPA ester]: d 5.20 (1H, dt, J = 1.2,
10.5 Hz, H-1a), 5.30 (1H, dt, J = 1.2, 17.3 Hz, H-1b) and
5.67 (1H, ddd, J = 6.8, 10.5, 17.3 Hz, H-2).
(c 1.0, CHCl3, >98% ee (S)). 1H NMR (400 MHz, CDCl3):
d 0.90 (3H, t, J = 7.1 Hz, H-8), 1.28–1.43 (4H, m, H-6 and
H-7), 1.62–1.76 (2H, m, H-5), 4.99–5.03 (1H, m, H-4), 6.08
(1H, dd, J = 1.9, 5.8 Hz, H-2), 7.42 (1H, dd, J = 1.5,
5.8 Hz, H-3). 13C NMR (100 MHz, CDCl3): d 13.8 (C-8),
22.4 (C-7), 27.0 (C-6), 32.9 (C-5), 83.4 (C-4), 121.5 (C-2),
156.2 (C-3), 174.4 (C-1). HR-FAB-MS: m/z 141.0918
([M+H]+, calcd for C8H13O2 m/z: 141.0916). IR (neat) m:
3088, 2958, 2933, 1752, 1601, 1163 cmꢀ1
.
4.10. (S)-Hept-2-en-4-olide (S)-14
4.6. (3S)-Oct-1-en-3-yl crotonate (S)-12
From (S)-11 (200 mg, 1.19 mmol) to (S)-14 (142 mg,
25
1.12 mmol, 93%). Colorless oil. ½aꢁD ¼ þ110:0 (c 1.16,
From rac-9 (500 mg, 3.91 mmol) to (S)-12 (352 mg,
1.80 mmol, 92% yield based on 50% conv., 99% ee). Color-
less oil. GC column temp.: 95 °C, tR: 31.6 min for (R)-12
CHCl3). 1H NMR (400 MHz, CDCl3): d 0.87 (3H, t,
J = 6.8 Hz), 1.34–1.44 (2H, m), 1.50–1.69 (2H, m), 4.96
(1H, dt, J = 1.8, 6.0 Hz), 5.99 (1H, dd, J = 1.8, 5.6 Hz),
7.41 (1H, d, J = 5.6 Hz). 13C NMR (100 MHz, CDCl3): d
13.5, 18.1, 34.9, 83.1, 121.1, 156.5, 173.0. HR-FAB-MS
m/z: 127.0756 ([M+H]+, calcd for C7H11O2 m/z:
127.0759). IR (neat) m: 3089, 2962, 2936, 2875, 1750,
26
1
and 32.8 min for (S)-12. ½aꢁD ¼ þ7:5 (c 1.19, CHCl3). H
NMR (400 MHz, CDCl3): d 0.85 (3H, t, J = 6.8 Hz),
1.23–1.33 (6H, m), 1.52–1.64 (2H, m), 1.85 (3H, dd,
J = 1.5, 6.8 Hz), 5.12 (1H, td, J = 1.2, 10.5 Hz), 5.20 (1H,
td, J = 1.2, 17.3 Hz), 5.25 (1H, tq, J = 1.2, 6.1 Hz), 5.77
(1H, ddd, J = 6.4, 10.5, 17.3 Hz), 5.83 (1H, qd, J = 1.5,
15.6 Hz), 6.96 (1H, qd, J = 6.8, 15.6 Hz). 13C NMR
(100 MHz, CDCl3): d 14.8, 18.8, 23.3, 25.5, 32.4, 35.0,
75.3, 117.1, 123.8, 137.6, 145.6, 166.7. HR-FAB-MS m/z:
197.1546 ([M+H]+, calcd for C12H21O2 m/z: 197.1542).
IR (neat) m: 3087, 3054, 3012, 2956, 2933, 2861, 1721,
1601, 1164 cmꢀ1
.
4.11. (S)-Non-2-en-4-olide (S)-15
From (S)-12 (119 mg, 0.607 mmol) to (S)-15 (88.1 mg,
25
0.570 mmol, 94%). Colorless oil. ½aꢁD ¼ þ94:0 (c 1.05,
25
CHCl3), lit.11 ½aꢁD ¼ þ85:53 (c 1.36, CHCl3, >99% ee (S)).
1658, 1181 cmꢀ1
.
1H NMR (400 MHz, CDCl3): d 0.82 (3H, t, J = 6.8 Hz),