J. J. De Voss et al.
(1H, m), 1.03 (3H, d, J1 =5.8 Hz), 1.05 (3H, d, J1 =5.9 Hz), 1.28–1.33
(16H, m), 1.51–1.65 (10H, m), 2.30 (4H, dt, J1 =1.4, 7.6 Hz), 2.85–2.92
(2H, m), 3.66 ppm (6H, s); 13C NMR (100 MHz, CDCl3): d (mixture of 2
isomers)=10.6, 10.8, 11.1, 11.2, 18.4, 18.7, 24.9, 25.57, 25.62, 26.7, 27.0,
29.0, 29.18, 29.21, 29.5, 34.0, 37.1, 37.4, 51.4, 76.4, 76.5, 174.3 ppm; GC-
MS (%): 200 (0.1), 158 (14.2), 143 (4.1), 115 (11.4), 101 (8.4), 98 (11.0),
87 (41.9), 85 (44.3), 74 (28.5), 67 (37.8), 57 (43.8), 55 (66.6), 43 (100), 41
(84.8); elemental analysis calcd (%) for C14H26O3: C 69.38, H 10.81;
found: C 69.39, H 10.74.
Methyl 10-methyldodec-9-enoate (10): Colourless oil; 1H NMR
(500 MHz, CDCl3): d=0.91 (5.10H, d, J1 =6.6 Hz), 0.93 (0.90H, d, J1 =
6.2 Hz), 1.20–1.35 (8H, m), 1.60 (2H, quint, J1 =7.5 Hz), 1.92 (0.3H, q,
J1 =6.6 Hz), 1.97 (1.7H, q, J1 =6.6 Hz), 2.27 (2H, t, J1 =7.5 Hz), 2.57
(1H, 2 octets, J1 =6.6 Hz), 3.64 (3H, s), 5.18 (1.85H, m), 5.32 ppm
(0.15H, m); 13C NMR (125 MHz, CDCl3, Z isomer only): d=22.7, 23.2,
24.9, 26.4, 27.2, 29.0, 29.1, 29.8, 34.1, 51.4, 127.4, 137.5, 174.3 ppm; GC-
MS (%): 226 [M+ ] (1.1), 194 (3.7), 152 (2.5), 139 (9.2), 74 (18.9), 69
C
(68.7), 55 (94.4), 41 (100); elemental analysis calcd (%) for C14H26O2: C
74.29, H 11.58; found: C 73.99, H 11.76.
Methyl 8-(E)-2-(1-hydroxyethyl)cyclopropyl)octanoate (5): Standard syn-
thesised as the methyl ester; colourless oil; 1H NMR (400 MHz, CDCl3,
mixture of 2 isomers): d=0.11 (2H, ddd, J1 =4.7, 8.4, 12.7 Hz), 0.20 (1H,
td, J1 =5.0, 8.3 Hz), 0.28 (1H, dt, J1 =4.7, 9.0 Hz), 0.45–0.6 (4H, m), 0.91–
1.35 (22H, m), 1.17 (3H, d, J1 =6.2 Hz), 1.19 (3H, d, J1 =6.2 Hz), 1.51–
1.60 (4H, m), 2.11 (4H, t, J1 =7.4 Hz), 2.92–2.99 (2H, m), 3.56 ppm (6H,
s); 13C NMR (100 MHz, C6D6): d (mixture of 2 isomers)=9.5 and 10.2,
22.9 and 23.0, 25.21 and 25.24, 27.3 and 27.4, 29.37 and 29.41, 29.54,
29.57, 29.61, 29.63, 29.8 and 29.9, 34.1, 50.9, 71.6, 173.4 ppm; GC-MS
For complete synthetic details see Supporting Information.
Acknowledgements
(%): 227 [M+ ꢀCH3] (0.2), 187 (1.8), 155 (25.4), 135 (5.6), 119 (18.3), 111
C
The authors would like to acknowledge financial support from the Aus-
tralian Research Council Grant DP110104455 (J.D.V.) and from the
Deutsche Forschungsgemeinschaft through the Emmy Noether Program
(M.J.C.).
(9.6), 98 (13.7), 87 (13.9), 83 (20.6), 74 (19.5), 69 (24.5), 67 (29.5), 55
(100), 45 (35.9), 43 (97.7), 41 (73.9); elemental analysis calcd (%) for
C14H26O3: C 69.38, H 10.81; found: C 69.18, H 10.91.
Methyl 12-hydroxytridec-9-enoate (6): Standard synthesised as the methyl
1
ester; colourless oil; H NMR (400 MHz, CDCl3): d=1.16 (2.25H, d, J1 =
[1] F. P. Guengerich, Curr. Drug Metab. 2001, 2, 93; M. J. Cryle, J. E.
6.0 Hz), 1.18 (0.75H, d, J1 =6.0 Hz), 1.20–1.40 (8H, m), 1.59 (2H, quint,
J1 =7.0 Hz), 1.86 (1H, brs), 2.00 (2H, quint, J1 =7.0 Hz), 2.05–2.20 (2H,
2 m), 2.27 (2H, t, J1 =7.4 Hz), 3.64 (3H, s), 3.70–3.85 (1H, m), 5.37 (1H,
m), 5.49 ppm (1H, m); 13C NMR (100 MHz, CDCl3, E isomer only): d=
22.6, 24.9, 28.9, 29.0, 29.1, 29.3, 32.6, 34.1, 42.5, 51.4, 67.2, 125.8, 134.6,
174.3 ppm; GC-MS (%): 224 [M+ꢀH2O] (0.4), 198 (2.4), 166 (7.9), 124
(11.7), 96 (19.5), 84 (23.2), 74 (40.8), 59 (18.5), 55 (62.5), 45 (100), 43
(49.1), 41 (59.0); elemental analysis calcd (%) for C14H26O3: C 69.38, H
10.81; found: C 69.37, H 11.04.
W. J. Ehlhardt, P. Kulanthaivel, D. L. Lanza, C. A. Reilly, G. S. Yost,
[6] M. J. Cryle, P. R. Ortiz de Montellano, J. J. De Voss, J. Org. Chem.
[7] M. J. Cryle, J. M. U. Stuthe, P. R. Ortiz de Montellano, J. J. De Voss,
[8] M. Newcomb, R. Shen, S.-Y. Choi, P. H. Toy, P. F. Hollenberg,
Newcomb, R. Shen, Y. Lu, M. J. Coon, P. F. Hollenberg, D. A. Kopp,
[9] L. A. Moe, Z. Hu, D. Deng, R. N. Austin, J. T. Groves, B. G. Fox, Bi-
[10] S. S. Boddupalli, B. C. Pramanik, C. A. Slaughter, R. W. Estabrook,
[11] D. C. Haines, D. R. Tomchick, M. Machius, J. A. Peterson, Biochem-
[12] S. S. Boddupalli, R. W. Estabrook, J. A. Peterson, J. Biol. Chem.
1990, 265, 4233; L. O. Narhi, A. J. Fulco, J. Biol. Chem. 1986, 261,
[13] H. M. Girvan, K. R. Marshall, R. J. Lawson, D. Leys, M. G. Joyce, J.
Clarkson, W. E. Smith, M. R. Cheesman, A. W. Munro, J. Biol.
Methyl tridec-9E,11-dienoate (7): Standard synthesised as the methyl
ester; colourless oil; 1H NMR (400 MHz, CDCl3): d=1.20–1.40 (8H, m),
1.58 (2H, m), 1.71 (2H, quint, J1 =10.0 Hz, J2 =1.6 Hz), 2.01 (1.16H, q,
J1 =7.0 Hz), 2.07 (0.84H, q, J1 =7.0 Hz), 2.27 (2H, t, J1 =7.2 Hz), 3.64
(3H, s), 5.34 (0.58H, d of q, J1 =10.8 Hz, J2 =7.0 Hz), 5.51 (0.84H, m),
5.63 (0.58H, d of t, J1 =15.0 Hz, J2 =7.5 Hz), 5.97 (1.42H, m), 6.29 ppm
(0.58H, d of d of q, J1 =15.0 Hz, J2 =10.8 Hz, J3 =1.2 Hz); 13C NMR
(100 MHz, CDCl3): d=13.2, 18.0, 24.9, 28.93, 28.98, 29.05, 29.08, 29.3,
29.7, 32.5, 32.8, 34.1, 51.4, 123.9, 125.4, 126.7, 129.5, 130.3, 131.7, 132.0,
134.4, 174.3 ppm; GC-MS (%): 224 [M+ ] (10.7), 192 (2.3), 150 (8.4), 95
C
(23.7), 81 (73.0), 68 (93.7), 67 (71.6), 41 (100); elemental analysis calcd
(%) for C14H24O2: C 74.95, H 10.78; found: C 74.67, H 10.94.
2-(2-Methyl-Z-cyclopropyl)-decanedioic acid, 10-methyl ester, 1-pyridine-
1
2-thione-N-oxycarbonyl ester (8): Yellow oil; H NMR (500 MHz, CDCl3,
Z isomer only): d=0.15 (1H, q, J1 =5.0 Hz), 0.79 (1H, m), 0.99 (2H, m),
1.03 (3H, d, J1 =6.0 Hz), 1.20–1.35 (7H, m), 1.49 (1H, m), 1.60 (2H,
quint, J1 =7.0 Hz), 1.70 (1H, m), 1.96 (1H, m), 2.27 (1H, m), 2.28 (2H, t,
J1 =7.5 Hz), 3.63 (3H, s), 7.67 (1H, t of d, J1 =7.0 Hz, J2 =1.9 Hz), 7.16
(1H, d of d of d, J1 =9.0 Hz, J2 =7.0 Hz, J3 =1.9 Hz), 7.48 (1H, d of d,
J1 =7.0 Hz, J2 =1.3 Hz), 7.67 ppm (1H, d of d of d, J1 =9.0 Hz, J2 =
1.9 Hz, J3 =0.6 Hz); 13C NMR (125 MHz, CDCl3, Z isomer only): d=
10.5, 11.5, 13.3, 18.6, 24.9, 27.2, 28.99, 29.02, 29.3, 32.7, 34.1, 43.1, 51.4,
112.5, 133.3, 137.5, 137.7, 171.8, 174.3, 176.0 ppm; GC-MS (%): 347 [M+
C
ꢀMeOH] (0.3), 335 (3.3), 302 (11.19), 138 (100), 136 (65.7), 112 (75.2),
111 (77.7), 78 (45.9), 67 (57.3), 41 (51.2); due to the light sensitivity of 8,
high resolution mass spectral data could not be obtained.
Methyl tridec-9-enoate (9): Colourless oil; 1H NMR (500 MHz, CDCl3):
d=0.86 (0.75H, t, J1 =7.5 Hz), 0.87 (2.25H, t, J1 =7.5 Hz), 1.25–1.40
(10H, m), 1.59 (2H, quint, J1 =7.3 Hz), 1.90–2.05 (4H, m), 2.28 (2H, t,
J1 =7.5 Hz), 3.64 (3H, s), 5.29–5.37 ppm (2H, m); 13C NMR (125 MHz,
CDCl3, E isomer only): d=13.8, 22.9, 24.9, 27.1, 29.05, 29.10, 29.12, 29.3,
29.6, 34.1, 51.4, 129.7, 129.9, 174.3 ppm; GC-MS (%): 226 [M+ ] (0.5), 194
C
(2.8), 152 (4.3), 110 (7.8), 74 (32.6), 67 (24.0), 55 (88.3), 41 (100); elemen-
tal analysis calcd (%) for C14H26O2: C 74.29, H 11.58; found: C 74.27, H
11.71.
15998
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 15994 – 15999