Transformation of Glycals into α,β,γ,δ-Conjugated Chirons
1 H), 7.21 (d, J = 7.4 Hz, 2 H), 6.98 (d, J = 15.1 Hz, 1 H), 6.49
(dd, J = 15.1, 11.2 Hz, 1 H), 6.03 (dd, J = 15.3, 6.9 Hz, 1 H), 5.60–
5.47 (m, 1 H), 5.26–5.11 (m, 1 H), 4.19 (dd, J = 12.0, 3.4 Hz, 1 H),
4.12 (dd, J = 12.1, 6.6 Hz, 1 H), 2.59 (t, J = 7.7 Hz, 2 H), 2.05 (s,
8.4, 2.4 Hz, 1 H), 6.91 (d, J = 15.1 Hz, 1 H), 6.48 (dd, J = 15.3,
11.1 Hz, 1 H), 6.04 (dd, J = 15.3, 6.5 Hz, 1 H), 5.55 (t, J = 5.9 Hz,
1 H), 5.22 (dd, J = 10.1, 5.8 Hz, 1 H), 4.28 (dd, J = 12.0, 4.2 Hz,
1 H), 3.98 (dd, J = 12.0, 6.4 Hz, 1 H), 2.08 (s, 3 H), 2.03 (s, 3 H),
3 H), 2.02 (s, 3 H), 1.99 (s, 3 H), 1.62–1.51 (m, 2 H), 1.25 (d, J = 2.00 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 188.9, 170.51,
3.0 Hz, 4 H), 0.82 (t, J = 6.4 Hz, 3 H) ppm. 13C NMR (125 MHz, 169.9, 169.6, 162.8, 139.8, 136.0, 132.2, 130.3, 126.8, 124.1, 120.0,
CDCl3): δ = 189.7, 170.5, 170.0, 169.6, 148.8, 141.8, 135.3, 134.9,
115.24, 71.4, 70.9, 61.9, 20.8, 20.79, 20.74 ppm. IR (neat): ν = 3453,
˜
132.8, 128.7 (2 C), 128.6 (2 C), 127.5, 71.8, 71.4, 61.7, 35.9, 31.4,
3075, 2925, 17446, 1586, 1372, 1221, 1046, 1020, 789, 723 cm–1.
30.7, 22.4, 20.9, 20.8, 20.7, 14.0 ppm. IR (neat): ν = 3471, 2957, HRMS (ESI+): calcd. for C20H22FO7 [M + H]+ 393.1350; found
˜
2930, 1747, 1664, 1607, 1371, 1222, 1048, 1025, 1013, 816, 795,
683 cm–1. HRMS (ESI+): calcd. for C25H32NaO7 [M + Na]+
467.2046; found 467.2022.
393.1362.
(6R,7R,2E,4E)-6,7,8-Tri-O-acetyl-1-(4-pentylphenyl)octa-2,4-diene-
1-one (12a): Prepared by general procedure 1 by using tri-O-acetyl-
d-galactal (0.5 mmol, 136 mg) and 4-pentylphenylacetylene
(0.55 mmol, 106 μL). Yield: 155 mg (70%). 1H NMR (400 MHz,
(6S,7R,2E,4E)-6,7,8-Tri-O-benzoyl-1-phenylocta-2,4-diene-1-one
(8a): Prepared by general procedure 1 by using tri-O-benzoyl-d-
glucal (0.5 mmol, 229 mg) and phenylacetylene (0.55 mmol, 58 μL). CDCl3): δ = 7.80 (d, J = 8.1 Hz, 2 H), 7.28 (dd, J = 15.1, 11.2 Hz,
1
Yield: 179 mg (64%). H NMR (400 MHz, CDCl3): δ = 7.94 (m, 6
H), 7.83 (d, J = 7.3 Hz, 2 H), 7.47 (m, 4 H), 7.42–7.26 (m, 9 H),
6.92 (d, J = 15.1 Hz, 1 H), 6.63 (dd, J = 15.2, 11.1 Hz, 1 H), 6.31
(dd, J = 15.3, 6.6 Hz, 1 H), 6.07–6.00 (m, 1 H), 5.78 (m, 1 H), 4.70
1 H), 7.21 (d, J = 8.1 Hz, 2 H), 6.96 (d, J = 15.1 Hz, 1 H), 6.48
(dd, J = 15.3, 11.2 Hz, 1 H), 5.99 (dd, J = 15.3, 6.6 Hz, 1 H), 5.55
(t, J = 6.0 Hz, 1 H), 5.21 (dd, J = 10.0, 5.8 Hz, 1 H), 4.29 (dd, J
= 12.0, 4.2 Hz, 1 H), 3.97 (dd, J = 12.0, 6.3 Hz, 1 H), 2.60 (t, J =
(dd, J = 12.0, 4.1 Hz, 1 H), 4.59 (dd, J = 12.0, 6.6 Hz, 1 H) ppm. 7.57 Hz, 2 H), 2.07 (s, 3 H), 2.03 (s, 3 H), 2.00 (s, 3 H), 1.61–1.54
13C NMR (125 MHz, CDCl3): δ = 190.2, 166.1, 165.5, 165.1, 142.2, (m, 2 H), 1.27–1.22 (m, 4 H), 0.82 (t, J = 6.6 Hz, 3 H) ppm. 13C
137.7, 133.6, 133.5, 133.3, 132.9, 132.8, 129.8, 129.7, 129.37, NMR (125 MHz, CDCl3): δ = 189.8, 170.5, 169.9, 169.7, 148.8,
129.34, 128.65, 128.64, 128.57, 128.50, 128.46, 127.5, 72.8, 72.1, 141.8, 135.3, 134.9, 132.6, 128.7 (2 C), 128.6 (2 C), 127.5, 71.5,
62.4 ppm. IR (neat): ν = 3438, 3062, 2925, 1723, 1664, 1634, 1600,
70.9, 61.9, 36.0, 31.4, 30.8, 22.5, 20.9, 20.8, 20.7, 14.0 ppm. IR
˜
1450, 1262, 1106, 1095, 710 cm–1. HRMS (ESI+): calcd. for (neat): ν = 3453, 3075, 2925, 1746, 1586, 1372, 1221, 1046, 1020,
˜
C35H28NaO7 [M + Na]+ 583.1733; found 583.1746.
789, 723 cm–1. HRMS (ESI+): calcd. for C25H32NaO7 [M + Na]+
467.2046; found 467.2034.
(6R,7R,2E,4E)-6,7,8-Tri-O-acetyl-1-phenylocta-2,4-diene-1-one
(9a): Prepared by general procedure 1 by using tri-O-acetyl-d-gal-
actal (0.5 mmol, 136 mg) and phenylacetylene (0.55 mmol, 56 μL).
(6R,7S,2E,4E)-6,7-Di-O-acetyl-1-phenylocta-2,4-diene-1-one (13a):
Prepared by general procedure 1 by using 3,4-di-O-acetyl-l-rham-
1
Yield: 125 mg (67%). H NMR (400 MHz, CDCl3): δ = 7.87 (d, J
nal (0.5 mmol, 107 mg) and phenylacetylene (0.55 mmol, 56 μL).
1
= 7.3 Hz, 2 H), 7.51 (t, J = 7.3 Hz, 1 H), 7.41 (t, J = 7.5 Hz, 2 H), Yield: 101 mg (64%). H NMR (400 MHz, CDCl3): δ = 7.95 (d, J
7.28 (dd, J = 15.0, 11.1 Hz, 1 H), 6.96 (d, J = 15.1 Hz, 1 H), 6.48
(dd, J = 15.2, 11.2 Hz, 1 H), 6.01 (dd, J = 15.3, 6.6 Hz, 1 H), 5.55
(t, J = 5.9 Hz, 1 H), 5.21 (dd, J = 10.1, 5.8 Hz, 1 H), 4.29 (dd, J
= 7.5 Hz, 2 H), 7.58 (t, J = 7.2 Hz, 1 H), 7.49 (t, J = 7.4 Hz, 2 H),
7.39 (dd, J = 14.8, 11.4 Hz, 1 H), 7.04 (d, J = 15.1 Hz, 1 H), 6.55
(dd, J = 14.7, 11.7 Hz, 1 H), 6.13 (dd, J = 15.3, 6.8 Hz, 1 H), 5.50
= 12.0, 4.1 Hz, 1 H), 3.98 (dd, J = 12.0, 6.3 Hz, 1 H), 2.07 (s, 3 (br. s, 1 H), 5.12 (m, 1 H), 2.13 (s, 3 H), 2.06 (s, 3 H), 1.24 (d, J =
H), 2.03 (s, 3 H), 2.00 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): 6.5 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 190.3, 170.3,
δ = 190.3, 170.5, 169.9, 142.3, 137.7, 135.3, 133.0, 132.5, 128.6 (2
169.9, 142.7, 137.7, 136.0, 132.9, 132.4, 128.6 (2 C), 128.4 (2 C),
C), 128.4 (2 C), 127.4, 71.5, 70.9, 61.9, 20.9, 20.8, 20.74 ppm. IR 126.9, 74.6, 70.4, 21.1, 21.0, 15.1 ppm. IR (neat): ν = 3462, 2932,
˜
(neat): ν = 3476, 3462, 2925, 1746, 1588, 1374, 1224, 1048, 1016, 1745, 1664, 1598, 1404, 1367, 1236, 1016, 1023, 772, 848, 601 cm–1.
˜
773, 698 cm–1. HRMS (ESI+): calcd. for C20H23O7 [M + H]+
375.1444; found 375.1458.
HRMS (ESI+): calcd. for C18H21O5 [M + H]+ 317.1389; found
317.1396.
(6R,7R,2E,4E)-6,7,8-Tri-O-acetyl-1-(p-tolyl)octa-2,4-diene-1-one (6R,7S,2E,4E)-6,7-Di-O-acetyl-1-(p-tolyl)octa-2,4-diene-1-one
(10a): Prepared by general procedure 1 by using tri-O-acetyl-d-
(14a): Prepared by general procedure 1 by using 3,4-di-O-acetyl-l-
glucal (0.5 mmol, 136 mg) and 4-methylphenylacetylene
rahmnal (0.5 mmol, 107 mg) and 4-methylphenylacetylene
(0.55 mmol, 69 μL). Yield: 135 mg (70 %). 1H NMR (400 MHz, (0.55 mmol, 69 μL). Yield: 102 mg (62 %). 1H NMR (400 MHz,
CDCl3): δ = 7.86 (d, J = 8.1 Hz, 2 H), 7.34 (dd, J = 15.0, 11.1 Hz,
1 H), 7.29 (br. s, 1 H), 7.27 (br. s, 1 H), 7.03 (d, J = 15.1 Hz, 1 H), 1 H), 7.21 (d, J = 7.2 Hz, 2 H), 6.97 (d, J = 15.1 Hz, 1 H), 6.51–
6.55 (dd, J = 15.3, 11.1 Hz, 1 H), 6.06 (dd, J = 15.3, 6.6 Hz, 1 H), 6.42 (m, 1 H), 6.04 (dd, J = 15.3, 6.8 Hz, 1 H), 5.42 (br. s, 1 H),
CDCl3): δ = 7.79 (d, J = 7.4 Hz, 2 H), 7.30 (dd, J = 14.5, 11.6 Hz,
5.62 (t, J = 5.9 Hz, 1 H), 5.28 (dd, J = 10.1, 5.9 Hz, 1 H), 4.36 (dd, 5.08–4.99 (m, 1 H), 2.35 (s, 3 H), 2.04 (s, 3 H), 1.98 (s, 3 H), 1.15
J = 12.0, 4.2 Hz, 1 H), 4.05 (dd, J = 12.0, 6.4 Hz, 1 H), 2.42 (s, 3 (d, J = 6.4 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 189.8,
H), 2.14 (s, 3 H), 2.10 (s, 3 H), 2.07 (s, 3 H) ppm. 13C NMR 170.3, 169.9, 143.8, 142.3, 135.7, 135.2, 132.5, 129.3 (2 C), 128.5 (2
(125 MHz, CDCl3): δ = 189.7,170.5, 169.9, 169.7, 143.9, 141.9,
C), 127.0, 74.6, 70.4, 21.6, 21.1, 21.0, 15.1 ppm. IR (neat): ν =
˜
135.1, 135.0, 132.6, 129.3 (2 C), 128.6 (2 C), 127.4, 71.5, 70.9, 61.9,
3455, 3074, 2935, 1741, 1666, 1682, 1600, 1408, 1369, 1238, 1180,
1023, 850, 604 cm–1. HRMS (ESI+): calcd. for C19H23O5 [M +
H]+ 331.1545; found 331.1523.
21.7, 20.9, 20.79, 20.74 ppm. IR (neat): ν = 3471, 2926, 1745, 1665,
˜
1599, 1371, 1224, 1047, 1016, 773, 698 cm–1. HRMS (ESI+): calcd.
for C21H24NaO7 [M + Na]+ 411.1420; found 411.1438.
(6R,7S,2E,4E)-6,7-Di-O-acetyl-1-(4-fluorophenyl)octa-2,4-diene-1-
(6R,7R,2E,4E)-6,7,8-Tri-O-acetyl-1-(3-fluorophenyl)octa-2,4-diene- one (15a): Prepared by general procedure 1 by using 3,4-di-O-
1-one (11a); Prepared by general procedure 1 by using tri-O-acetyl-
d-galactal (0.5 mmol, 136 mg) and 3-fluorophenylacetylene
acetyl-l-rahmnal (0.5 mmol, 107 mg) and 4-fluorophenylacetylene
(0.55 mmol, 63 μL). Yield: 103 mg (62%). 1H NMR (400 MHz,
(0.55 mmol, 63 μL). Yield: 129 mg (66 %). 1H NMR (400 MHz, CDCl3): δ = 7.97–7.85 (m, 2 H), 7.31 (dd, J = 14.6, 11.5 Hz, 1 H),
CDCl3): δ = 7.65 (d, J = 7.7 Hz, 1 H), 7.56 (d, J = 9.3 Hz, 1 H),
7.40 (dd, J = 13.5, 7.9 Hz, 1 H), 7.34–7.25 (m, 1 H), 7.22 (dd, J =
7.08 (t, J = 7.9 Hz, 2 H), 6.94 (d, J = 15.0 Hz, 1 H), 6.53–6.40 (m,
1 H), 6.06 (dd, J = 15.3, 6.8 Hz, 1 H), 5.42 (br. s, 1 H), 5.05 (br. s,
Eur. J. Org. Chem. 2014, 7333–7338
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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