J.-L. Débieux, A. Cosandey, C. Helgen, C. G. Bochet
FULL PAPER
61.0 (CH ), 56.3 (2ϫCH ), 21.2 (CH ) ppm. IR (neat): ν = 2999,
(؎)-Linaloyl Acetate (4j): Purification by flash column chromatog-
raphy [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz, CDCl3): δ
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2943, 1740, 1593, 1508, 1463, 1424, 1364, 1332, 1237, 1129,
1010 cm–1. MS (ESI): m/z (%) = 263.1 (100) [M + Na]+. HRMS: = 6.01–5.93 (m, 1 H), 5.17,5.07 (m, 3 H), 2.01 (s, 3 H), 1.96 (t, J
calcd. for C12H16O5 240.0998; found 240.0999.
= 7.5 Hz, 2 H), 1.89–1.71 (m, 2 H), 1.67 (s, 3 H), 1.59 (s, 3 H), 1.53
(s, 3 H) ppm. 13C NMR (90.55 MHz, CDCl3) δ = 170.0 (C), 141.8
(CH), 131.8 (C), 123.8 (CH), 113.1 (CH2), 82.9 (C), 39.7 (CH2),
25.7 (CH3), 23.6 (CH3), 22.3 (CH2), 22.2 (CH3), 17.6 (CH3) ppm.
(–)-Menthyl Acetate (4e): Purification by flash column chromatog-
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raphy [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz, CDCl3): δ
= 4.66 (td, J = 10.9, 4.1 Hz, 1 H), 2.03 (s, 3 H), 2.00–1.95 (m, 1
H), 1.92–1.79 (m, 1 H), 1.71–1.63 (m, 2 H), 1.55–1.41 (m, 1 H),
1.39–1.31 (m, 1 H), 1.11–0.94 (m, 2 H), 0.9–0.88 (m, 7 H), 0.77–
0.75 (d, 3 H) ppm. 13C NMR (90.55 MHz, CDCl3): δ = 170.8 (C),
74.2 (CH), 47.0 (CH), 40.9 (CH2), 34.2 (CH2), 31.4 (CH), 26.3
(CH), 23.5 (CH2), 22.0 (CH3), 21.3 (CH3), 20.7 (CH3), 16.4 (CH3)
IR (neat): ν = 2973, 2930, 2861, 1740, 1450, 1370, 1248, 1173, 1093,
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1019, 922 cm–1. HRMS: calcd. for C12H20O2 196.1463; found
196.1458.
Geranyl Acetate (4k): Purification by flash column chromatography
[SiO2, hexane/EtOAc (9:1)]. 1H NMR (360 MHz, CDCl3): δ = 5.34
(t, J = 7.2 Hz, 1 H), 5.08 (t, J = 6.8 Hz, 1 H), 4.58 (d, J = 7.3 Hz,
2 H), 2.14–2.00 (m, 4 H), 2.05 (s, 3 H), 1.70 (s, 3 H), 1.68 (s, 3 H),
1.60 (s, 3 H) ppm. 13C NMR (90.55 MHz, CDCl3): δ = 171.2 (C),
142.3 (C), 131.8 (C), 123.7 (CH), 118.2 (CH), 61.4 (CH2), 39.5
(CH2), 26.3 (CH2), 25.7 (CH3), 21.1 (CH3), 17.7 (CH3), 16.5 (CH3)
ppm. IR (neat): ν = 2957, 2932, 2871, 1737, 1457, 1371, 1246,
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1025 cm–1. MS (ESI): m/z (%) = 221.1 (100) [M + Na]+. HRMS:
calcd. for C12H22O2 198.1620; found 198.1614.
2-Oxo-1,2-diphenylethyl Acetate (4f): The crude product was tritu-
rated with EtOAc. Evaporation of EtOAc gave the ester, the re-
maining alcohol and 5,7-dinitroindoline. Purification by flash col-
umn chromatography [SiO2, hexane/EtOAc (6:1)]. 1H NMR
(360 MHz, CDCl3): δ = 7.93 (d, J = 7.2 Hz, 2 H), 7.53–7.32 (m, 8
H), 6.86 (s, 1 H), 2.21 (s, 3 H) ppm. 13C NMR (90.55 MHz,
CDCl3): δ = 193.7 (C), 170.5 (C), 134.6 (C), 133.6 (C), 133.5 (CH),
129.3 (CH), 129.1 (2ϫCH), 128.8 (2ϫCH), 128.7 (2ϫCH), 128.6
ppm. IR (neat): ν = 2969, 2926, 2859, 1742, 1446, 1380, 1369, 1233,
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1024, 982, 955 cm–1. MS (ESI): m/z (%) = 219.1 (100) [M + Na]+.
HRMS: calcd. for C12H20O2 196.1463; found 196.1457.
1-Ethynylcyclohexyl Acetate (4l): Purification by flash column
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chromatography [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz,
CDCl3): δ = 2.60 (s, 1 H), 2.16–2.10 (m, 2 H), 2.05 (s, 3 H), 1.88–
1.81 (m, 2 H), 1.65–1.59 (m, 4 H), 1.55–1.48 (m, 1 H), 1.38–1.27
(m, 1 H) ppm. 13C NMR (90.55 MHz, CDCl3): δ = 169.3 (C), 83.7
(C), 75.1 (C), 74.2 (CH), 36.9 (2ϫH2), 25.1 (CH2), 22.4 (2ϫCH2),
(2ϫCH), 77.6 (CH), 20.8 (CH ) ppm. IR (neat): ν = 1740, 1697,
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1598, 1451, 1374, 1231, 1182, 1056, 1005, 973, 932, 758, 699,
526 cm–1. MS (ESI): m/z (%) = 277.1 (100) [M + Na]+. HRMS:
calcd for C16H14O3 254.0943; found 254.0942.
21.9 (CH ) ppm. IR (neat): ν = 3283, 2934, 2863, 2113, 1745, 1450,
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1368, 1231, 1145, 1025, 957, 663 cm–1. GC–MS: m/z (%) = 166.1
(2) [M]+, 124.0 (58), 109 (40), 106 (50), 95 (74), 91 (10), 81 (92), 79
(68), 67 (52). HRMS: calcd. for C10H14O2 166.0994; found
160.0983.
1-Formylnaphthalen-2-yl Acetate (4 g): The crude product was tritu-
rated with EtOAc. Evaporation of EtOAc gave the ester, the re-
maining alcohol and 5,7-dinitroindoline. Purification by flash col-
umn chromatography [SiO2, hexane/EtOAc (6:1)]. 1H NMR
(360 MHz, CDCl3): δ = 10.71 (s, 1 H), 9.14 (d, J = 8.6 Hz, 1 H),
8.10 (d, J = 9.1 Hz, 1 H), 7.88 (d, J = 8.2 Hz, 1 H), 7.68 (t, J =
7.3 Hz, 1 H), 7.56 (t, J = 7.5 Hz, 1 H), 7.28 (d, J = 9.6 Hz, 1 H),
2.44 (s, 3 H) ppm. 13C NMR (90.55 MHz, CDCl3): δ = 190.0 (C),
169.2 (C), 154.4 (C), 136.5 (CH), 131.8 (C), 131.1 (C), 129.6 (CH),
128.5 (CH), 126.7 (CH), 125.0 (CH), 121.6 (CH), 121.4 (C), 20.9
1,2,3,4,6-Penta-O-acetyl-β-D-glucose (4m): The crude product was
triturated with EtOAc. Evaporation of EtOAc gave the ester, the
remaining alcohol and 5,7-dinitroindoline. Purification by flash col-
umn chromatography (SiO2, CH2Cl2) to remove 5,7-dinitroindol-
1
ine and [SiO2, hexane/EtOAc (1:1)]. H NMR (360 MHz, CDCl3):
δ = 5.71 (d, J = 8.2 Hz, 1 H), 5.25 (dd, J = 9.3 Hz, 1 H), 5.15–5.10
(m, 2 H), 4.29 (dd, J = 12.5, 4.3 Hz, 1 H), 4.11 (dd, J = 12.5,
2.1 Hz, 1 H), 3.84 (dm, J = 10 Hz, 1 H), 2.11 (s, 3 H), 2.08 (s, 3 H),
2.03 (s, 6 H), 2.01 (s, 3 H) ppm. 13C NMR (90.55 MHz, CDCl3): δ
= 170.6 (C), 170.1 (C), 169.4 (C), 169.2 (C), 169.0 (C), 91.7 (CH),
72.7 (2ϫCH), 70.2 (CH), 67.7 (CH), 61.4 (CH2), 20.8 (CH3), 20.7
(CH ) ppm. IR (KBr): ν = 1767, 1688, 1617, 1576, 1511, 1434,
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1372, 1342, 1189, 1161, 1061, 1036, 1017, 979, 893, 857, 826, 763,
743, 706, 675, 510 cm–1. MS (ESI): m/z (%) = 237.0 (100) [M +
Na]+. HRMS: calcd for C13H10O3 214.0630; found 214.0625.
(CH ), 20.6 (3ϫCH ) ppm. IR (neat/CHCl ): ν = 3025, 1760, 1370,
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3
3
3
Cyclohexyl Acetate (4h): Purification by flash column chromatog-
raphy [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz, CDCl3): δ
= 4.76–4.70 (m, 1 H), 2.03 (s, 3 H), 1.87–1.82 (m, 2 H), 1.74–1.70
(m, 2 H) 1.57–1.52 (m, 1 H), 1.44–1.20 (m, 5 H) ppm. 13C NMR
(90.55 MHz, CDCl3): δ = 170.6 (C), 72.7 (CH), 31.6 (2ϫCH2),
1222, 1080, 1040, 758, 669 cm–1. HRMS: calcd. for C16H22O11
1
390.1162; found 390.1156.
(؎)-1-Phenylethyl Acetate (4n): Purification by flash column
1
chromatography [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz,
25.4 (CH ), 23.8 (2ϫCH ), 21.5 (CH ) ppm. IR (neat): ν = 2940,
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CDCl3): δ = 7.36–7.28 (m, 5 H), 5.88 (q, J = 6.8 Hz, 1 H), 2.08 (s,
3 H), 1.54 (d, J = 6.8 Hz, 3 H) ppm. 13C NMR (90.55 MHz,
CDCl3): δ = 170.3 (C), 141.7 (C), 128.5 (2ϫCH), 127.9 (CH), 126.1
2861, 1737, 1452, 1379, 1364, 1241, 1126, 1046, 1023, 968, 907,
735 cm–1. MS (ESI): m/z (%) = 286.3 {2ϫ[M + H]+}, 165.1 (40)
[M + Na]+.
(2ϫCH), 72.3 (CH), 22.2 (CH ), 21.4 (CH ) ppm. IR (neat): ν =
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3
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3065, 3034, 2983, 2936, 1744, 1495, 1453, 1372, 1242, 1210, 1065,
1027, 945, 761, 700, 539 cm–1. HRMS: calcd. for C10H12O2
164.0837; found 164.0831.
trans-(–)-Myrtyl Acetate (4i): Purification by flash column
chromatography [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz,
CDCl3): δ = 3.92–3.81 (m, 2 H), 2.34–2.25 (m, 1 H), 2.08–2.02 (m,
1
1 H), 2.03 (s, 3 H), 1.89–1.71 (m, 4 H), 1.67–1.59 (m, 1 H), 1.34– Cinnamyl Acetate (4o): Purification by flash column chromatog-
1
1.18 (m, 2 H), 1.21 (s, 3 H), 0.84 (s, 3 H) ppm. 13C NMR raphy [SiO2, hexane/EtOAc (9:1)]. H NMR (360 MHz, CDCl3): δ
(90.55 MHz, CDCl3) δ = 171.4 (C), 68.0 (CH2), 42.3 (CH), 40.8 = 7.40 (d, J = 7.3 Hz; 2 H), 7.33 (dd, J = 7.3 Hz, 2 H), 7.26 (dd,
(CH), 39.1 (C), 34.1 (CH), 26.6 (CH2), 23.9 (CH3), 23.3 (CH2),
J = 7.1 Hz, 1 H), 6.66 (d, J = 15.9 Hz, 1 H), 6.29 (dt, J = 15.9,
21.0 (CH ), 20.1 (CH ), 18.1 (CH ) ppm. IR (neat): ν = 2979, 2945,
6.6 Hz, 1 H), 4.73 (d, J = 6.4 Hz, 2 H), 2.10 (s, 3 H) ppm. 13C
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2917, 2870, 1743, 1463, 1386, 1367, 1236, 1031, 980 cm–1. MS NMR (90.55 MHz, CDCl3): δ = 170.9 (C), 136.2 (C), 134.2 (CH),
(ESI): m/z (%) = 219.1 (100) [M + Na]+. HRMS: calcd. for
128.6 (2ϫCH), 128.1 (CH), 126.6 (2ϫCH), 123.1 (CH), 65.1
(CH ), 21.0 (CH ) ppm. IR (neat): ν = 3060, 3029, 2945, 1739,
C12H20O2 196.1463; found 196.1456.
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Eur. J. Org. Chem. 2007, 2073–2077