ChemSusChem
10.1002/cssc.201801463
FULL PAPER
evaporated. Purification was performed using column chromatography
1.42 (m, 1H), 1.42 – 1.10 (m, 10H), 0.92 (d, J = 6.5 Hz, 0.16 x 3H), 0.84
(20% toluene in c-hex).
(d, J = 6.6 Hz, 0.84 x 3H); 13C NMR (101 MHz, CDCl
3
): δ (ppm) 174.0,
(
10E/Z)-oxacyclononadec-10-en-2-one (7)
174.0, 131.0, 130.6, 130.5, 129.8, 62.2, 61.8, 36.6, 36.5, 36.4, 35.9, 35.2,
34.7, 31.3, 29.5, 29.0, 28.7, 28.4, 28.3, 28.1, 27.6, 27.5, 27.1, 26.8, 26.4,
26.4, 25.5, 25.1, 24.7, 19.5, 17.2. The spectra correspond to those
described in the literature.8
(10E/Z,14E)-14-methyloxacyclohexadec-10,14-dien-2-one (24)
Method A. Lactone 24 was prepared according to a general procedure
from (E)-3,7-dimethyloct-6-en-1-yl dec-9-enoate (14) (0.15 g, 0.49 mmol).
Nitro-Hoveyda catalyst (6.6 mg, 9.8 μmol), tetrafluoro-1,4-benzoquinone
(3.5 mg, 19.7 μmol) and 328 mL of toluene were used to afford
macrocycle 24 as a colourless oil with musk scent (99 mg, 0.39 mmol,
80% yield, E/Z = 3.1/1).
Method B. Lactone 24 was prepared according to a general procedure
from (E)-3,7-dimethyloct-6-en-1-yl oleate (15) (0.15 g, 0.36 mmol). Nitro-
Hoveyda catalyst (4.8 mg, 7.2 μmol), tetrafluoro-1,4-benzoquinone (2.6
mg, 14.4 μmol) and 240 mL of toluene were used to afford macrocycle 24
as a colourless oil with musk scent (43 mg, 0.17 mmol, 48% yield, E/Z =
Method A. Lactone 7 was prepared according to a general procedure
from dec-9-en-1-yl dec-9-enoate (3) (0.15 g, 0.49 mmol). Nitro-Hoveyda
catalyst (6.6 mg, 9.8 μmol), tetrafluoro-1,4-benzoquinone (3.6 mg, 19.6
μmol) and 327 mL of toluene were used to afford macrocycle 7 as a
colourless oil with musk scent (106 mg, 0.38 mmol, 77% yield, E/Z =
3
.6/1).
Method B. Lactone 7 was prepared according to a general procedure
from oleyl oleate (6) (0.15 g, 0.28 mmol). Nitro-Hoveyda catalyst (3.8 mg,
5
of toluene were used to afford macrocycle 7 as a colourless oil with musk
scent (29 mg, 0.10 mmol, 38% yield, E/Z = 3.9/1).
Method C. Lactone 7 was prepared according to a general procedure
from dec-9-en-1-yl oleate (8) (0.15 g, 0.36 mmol). Nitro-Hoveyda catalyst
.6 μmol), tetrafluoro-1,4-benzoquinone (2,0 mg, 11,2 μmol) and 190 mL
(4.8 mg, 7.2 μmol), tetrafluoro-1,4-benzoquinone (2.6 mg, 14.4 μmol) and
2
40 mL of toluene were used to afford macrocycle 7 as a colourless oil
with musk scent (90 mg, 0.32 mmol, 89% yield, E/Z = 4.2/1).
3.0/1).
1
Method D. Lactone 7 was prepared according to a general procedure
from (Z)-octadec-9-en-1-yl dec-9-enoate (9) (0.15 g, 0.36 mmol). Nitro-
Hoveyda catalyst (4.8 mg, 7.2 μmol), tetrafluoro-1,4-benzoquinone (2.6
mg, 14.4 μmol) and 240 mL of toluene were used to afford macrocycle 7
as a colourless oil with musk scent (92 mg, 0.33 mmol, 92% yield, E/Z =
3
H NMR (400 MHz, CDCl ): δ (ppm) 5.47 – 5.20 (m, 3H), 4.56 (m, 2H),
2.39 – 2.29 (m, 2H), 2.24 – 2.08 (m, 4H), 2.05 – 1.91 (m, 2H), 1.75 –
1.53 (m, 5H), 1.36 – 1.25 (m, 8H); 13C NMR (101 MHz, CDCl
): δ (ppm)
174.0, 173.9, 142.3, 140.6, 130.9, 130.1, 130.1, 129.5, 119.9, 118.6,
61.3, 61.2, 39.3, 39.0, 35.0, 34.4, 31.4, 29.0, 28.3, 27.9, 27.8, 27.7, 27.7,
27.6, 27.1, 27.0, 26.9, 26.3, 24.8, 24.3, 17.2, 15.5; IR (film): 2967, 2925,
2856, 2802, 1729, 1609, 1520, 1488, 1441, 1357, 1222, 1188, 1113,
1089, 1015, 973, 814; HRMS ([M+H]+): calculated for
251.2006, found: 251.2002; Elemental analysis: calculated for
16 26 2
C H O : C 76.75, H 10.47; found: C 76.56, H 10.35.
(10E/Z,14Z)-14-methyloxacyclohexadec-10,14-dien-2-one (25)
Method A. Lactone 25 was prepared according to a general procedure
from (Z)-3,7-dimethyloct-6-en-1-yl dec-9-enoate (16) (0.15 g, 0.49 mmol).
Nitro-Hoveyda catalyst (6.6 mg, 9.8 μmol), tetrafluoro-1,4-benzoquinone
(3.5 mg, 19.7 μmol) and 328 mL of toluene were used to afford
macrocycle 25 as a colourless oil with musk scent (107 mg, 0.43 mmol,
87% yield, E/Z = 6.8/1).
Method B. Lactone 25 was prepared according to a general procedure
from (Z)-3,7-dimethyloct-6-en-1-yl oleate (17) (0.15 g, 0.36 mmol). Nitro-
Hoveyda catalyst (4.8 mg, 7.2 μmol), tetrafluoro-1,4-benzoquinone (2.6
mg, 14.4 μmol) and 240 mL of toluene were used to afford macrocycle 25
as a colourless oil with musk scent (36 mg, 0.14 mmol, 40% yield, E/Z =
3
4
.2/1).
1
H NMR (400 MHz, (CDCl
3
) δ (ppm) 5.53 – 5.16 (m, 2H), 4.15 – 4.05 (m,
H), 2.31 (td, J = 7.0, 5.3 Hz, 2H), 2.12 – 1.91 (m, 4H), 1.72 – 1.54 (m,
H), 1.47 – 1.15 (m, 16H); 13C NMR (101 MHz, CDCl
): δ (ppm) 174.3,
74.2, 131.0, 131.0, 130.4, 130.3, 64.7, 64.4, 35.2, 35.1, 32.3, 29.8, 29.7,
9.5, 29.5, 29.4, 29.3, 29.3, 29.3, 29.3, 29.2, 29.1, 29.0, 29.0, 28.2, 28.0,
7.9, 27.3, 26.5, 26.5, 26.3, 25.5, 25.5. The spectra correspond to those
2
4
1
2
2
16 27 2
C H O :
3
described in the literature.10
10E/Z)-oxacycloheptadec-10-en-2-one (22)
(
Method A. Lactone 22 was prepared according to a general procedure
from oct-7-en-1-yl dec-9-enoate (10) (0.15 g, 0.54 mmol). Nitro-Hoveyda
catalyst (7.2 mg, 10.7 μmol), tetrafluoro-1,4-benzoquinone (3.9 mg, 21.4
μmol) and 356 mL of toluene were used to afford macrocycle 22 as a
colourless oil with musk scent (104 mg, 0.41 mmol, 77% yield, E/Z =
2.2/1).
Method B. Lactone 22 was prepared according to a general procedure
from oct-7-en-1-yl oleate (11) (0.15 g, 0.39 mmol). Nitro-Hoveyda
catalyst (5.2 mg, 7.7 μmol), tetrafluoro-1,4-benzoquinone (2.8 mg, 15.4
μmol) and 256 mL of toluene were used to afford macrocycle 22 as a
colourless oil with musk scent (87 mg, 0.35 mmol, 90% yield, E/Z = 2.2/1).
5.1/1).
1
3
H NMR (400 MHz, CDCl ): δ (ppm) 5.48 – 5.25 (m, 3H), 4.64 – 4.48 (m,
2H), 2.39 – 2.32 (m, 2H), 2.26 – 2.10 (m, 4H), 2.02 – 1.92 (m, 2H), 1.84 –
1.58 (m, 5H), 1.37 – 1.24 (m, 8H); 13C NMR (101 MHz, CDCl
): δ (ppm)
174.4, 174.3, 145.7, 141.4, 131.1, 130.6, 129.4, 129.1, 120.0, 118.3,
60.9, 60.8, 34.3, 33.8, 32.3, 31.0, 31.0, 29.3, 27.6, 27.3, 27.3, 27.2, 27.2,
26.9, 26.6, 26.6, 26.1, 25.8, 24.9, 24.5, 24.2, 22.5; IR (film): 2926, 2854,
1H NMR (400 MHz, CDCl
): δ (ppm) 5.43 – 5.27 (m, 2H), 4.20 – 4.02 (m,
H), 2.38 – 2.25 (m, 2H), 2.03 (m, 4H), 1.61 (m, 4H), 1.45 – 1.20 (m,
4H); 13C NMR (101 MHz, CDCl
): δ (ppm) 174.2, 174.1, 131.3, 130.7,
3
3
2
1
1
2
2
3
30.5, 130.2, 64.5, 64.5, 35.1, 31.9, 31.5, 29.8, 29.3, 29.0, 28.8, 28.7,
8.7, 28.6, 28.3, 28.1, 28.1, 28.0, 27.9, 27.1, 26.9, 26.6, 26.1, 25.9, 25.3,
5.2. The spectra correspond to those described in the literature.11
+
1731, 1441, 1380, 1350, 1258, 1083, 1024, 801; HRMS ([M+H] ):
calculated for
16 27 2
C H O :
251.2006, found: 251.2005; Elemental
(10E/Z)-14-methyloxacyclohexadec-10-en-2-one (23)
analysis: calculated for C16H O : C 76.75, H 10.47; found: C 76.88, H
26 2
Method A. Lactone 23 was prepared according to a general procedure
from 3,7-dimethyloct-6-en-1-yl dec-9-enoate (12) (0.15 g, 0.51 mmol).
Nitro-Hoveyda catalyst (6.5 mg, 9.7 μmol), tetrafluoro-1,4-benzoquinone
10.25.
(10E/Z)-oxacyclohexadec-10-en-2-one (26)
Method A. Lactone 26 was prepared according to a general procedure
from (Z)-non-6-en-1-yl dec-9-enoate (18) (0.15 g, 0.51 mmol). Nitro-
Hoveyda catalyst (6.9 mg, 10.2 μmol), tetrafluoro-1,4-benzoquinone (3.8
mg, 20.4 μmol) and 340 mL of toluene were used to afford macrocycle 26
as a colourless oil with musk scent (106 mg, 0.45 mmol, 87% yield, E/Z =
4.6/1).
Method B. Lactone 26 was prepared according to a general procedure
from (Z)-non-6-en-1-yl oleate (19) (0.15 g, 0.37 mmol). Nitro-Hoveyda
catalyst (4.9 mg, 7.4 μmol), tetrafluoro-1,4-benzoquinone (2.7 mg, 14.8
μmol) and 247 mL of toluene were used to afford macrocycle 26 as a
colourless oil with musk scent (80 mg, 0.34 mmol, 91% yield, E/Z = 3.6/1).
(
3.6 mg, 19.4 μmol) and 323 mL of toluene were used to afford
macrocycle 23 as a colourless oil with musk scent (107 mg, 0.43 mmol,
8% yield, E/Z = 5.8/1).
8
Method B. Lactone 23 was prepared according to a general procedure
from 3,7-dimethyloct-6-en-1-yl oleate (13) (0.15 g, 0.36 mmol). Nitro-
Hoveyda catalyst (4.8 mg, 7.4 μmol), tetrafluoro-1,4-benzoquinone (2.6
mg, 14.4 μmol) and 240 mL of toluene were used to afford macrocycle 23
as a colourless oil with musk scent (44 mg, 0.17 mmol, 48% yield, E/Z =
4
.7/1).
1
H NMR (400 MHz, CDCl
3
): δ (ppm) 5.41 – 5.27 (m, 2H), 4.24 – 4.06 (m,
2H), 2.44 – 2.21 (m, 2H), 2.19 – 1.92 (m, 4H), 1.76 – 1.56 (m, 4H), 1.53 –
This article is protected by copyright. All rights reserved.