Supporting Information

Supporting Information Wiley-VCH 2012 69451 Weinheim, Germany Concise Syntheses of Insect Pheromones Using Z-Selective Cross Metathesis** Myles B. Herbert, Vanessa M. Marx, Richard L. Pederson, and Robert H. Grubbs* anie_201206079_sm_miscellaneous_information.pdf

Table of Contents Procedures and spectral data General methods Compounds 3, 5, and 6 Compounds 7 and 8 Compounds 9 and 10 Compounds 12, 13, and 15 Compounds 16 and 18 Compounds 19, 20, and 21 Compounds 22 and (±)-24 General Procedure for Time Course Experiment S1 S9 S1 S2 S3 S4 S5 S6 S7 S8 S9 1 H and 13 C NMR spectra including COSY spectrum of S10 S53 compound 15 and HSQC spectra for compounds 3, 5, 7, 9, 12, 15, 19, 21, and (±)-24. General methods All reactions were carried out in dry glassware under an argon atmosphere using standard Schlenk techniques or in a Vacuum Atmospheres Glovebox under a nitrogen atmosphere, unless otherwise specified. All solvents were purified by passage through solvent purification columns and further degassed by bubbling argon. NMR solvents were dried over CaH 2 and vacuum transferred to a dry Schlenk flask and subsequently degassed with bubbling argon. C 6 D 6 was purified by passage through a solvent purification column. CDCl 3 was used as received. All α-olefins were filtered through a plug of neutral alumina prior to use. Ruthenium complex 1 was obtained from Materia Inc. 11-eiosenol (4) was synthesized from Jojoba oil. 1 Other commercially available reagents and silica gel were used as received. 1 H NMR spectra were acquired at 500 MHz and 13 C NMR spectra at 125 MHz as CDCl 3 solutions unless otherwise noted. Quantitative 13 C measurements were acquired at 100 MHz (decoupled, without NOE, 15 second delay time). High-resolution mass spectra (HRMS) were provided by the California Institute of Technology Mass Spectrometry Facility using a JEOL JMS-600H High Resolution Mass Spectrometer. All HRMS were by positive-ion EI or FAB. All cross metathesis reactions involving the seed oil derivatives 2 and 4 required purification by multiple columns to separate the desired products from the starting material and any terminal olefins generated. 1 R.L. Pederson, I. M. Fellows, T. A. Ung, H. Ishihara, S. P. Hajela, Adv. Synth. Catal. 2002, 344, 728. S1

(Z)-Tetradec-9-en-1-ol (3) In a glovebox, a 20 ml vial was charged with oleyl alcohol (1.0 g, 3.7 mmol), 1-hexene (4 ml), and THF (4 ml). A solution of 1 (0.023 g, 1 mol%) in THF (0.5 ml) was added, and the mixture was stirred in an open vial for 5 hours. The vial was removed from the glovebox, the reaction was quenched with excess ethyl vinyl ether, and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, using a gradient of hexanes to 20% EtOAc in hexanes) provided 3 (0.73 g, 77% yield, 86% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.35 (2H, m), 3.64 (2H, td, J = 6.6, 5.3 Hz), 2.02 (4H, m), 1.57 (2H, m), 1.22-1.39 (15H, m), 0.90 (3H, t, J = 7.1 Hz); 13 C NMR (CDCl 3 ): δ 129.9, 129.8, 63.1, 32.8, 32.0, 29.8, 29.5, 29.4, 29.2, 27.2, 26.9, 25.7, 22.4, 14.0; HRMS (FAB): 213.2215, [C 14 H 28 O+H] + requires 213.2218. (Z)-Hexadec-11-en-1-ol (5) According to the procedure for compound 3, 11-eicosenol (1.3 g, 4.4 mmol) and 1-hexene (6 ml) in THF (6 ml) were reacted with 1 (0.028 g, 1 mol%) to provide 5 (0.84 g, 76% yield, 86% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.36 (2H, m), 3.64 (2H, td, J = 6.5, 5.3 Hz), 2.02 (4H, m), 1.56 (2H, m), 1.23-1.38 (19H, m), 0.90 (3H, t, J = 7.2 Hz); 13 C NMR (CDCl 3 ): δ 129.9 (2C), 63.1, 32.8, 32.0, 29.8, 29.6 (2C), 29.5, 29.4, 29.3, 27.2, 26.9, 25.8, 22.4, 14.0; HRMS (FAB): 241.2536, [C 16 H 32 O+H] + requires 241.2531. (Z)-Hexadec-11-enal (6) DMSO (0.11 ml, 1.6 mmol) was added dropwise to a solution of oxalyl chloride (0.080 ml, 0.96 mmol) in CH 2 Cl 2 (5 ml) at -78 C, and after 5 minutes a solution of alcohol 5 (0.21 g, 0.87 mmol) in CH 2 Cl 2 (0.9 ml) was added. After stirring for 15 minutes at the same temperature, triethylamine (0.61 S2

ml, 4.4 mmol) was added. The mixture was warmed to room temperature, diluted with Et 2 O, washed sequentially with 1M HCl, saturated aqueous NaHCO 3, brine, dried with Na 2 SO 4, and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, 10% EtOAc in hexanes) provided 6 (0.20 g, 95% yield, 86% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 9.76 (1H, t, J = 1.9 Hz), 5.36 (2H, m), 2.42 (2H, td, J = 7.4, 1.9 Hz), 2.02 (4H, m), 1.63 (2H, m), 1.24-1.36 (16H, m), 0.90 (3H, t, J = 7.2 Hz); 13 C NMR (CDCl 3 ): δ 202.9, 129.9, 129.8, 43.9, 32.0, 29.8, 29.5, 29.4 (2C), 29.3, 29.2, 27.2, 26.9, 22.4, 22.1, 14.0; HRMS (FAB): 237.2209, [C 16 H 30 O-H] + requires 237.2218. (Z)-Dodec-9-en-1-ol (7) In a glovebox, a 25 ml Schlenk flask was charged with oleyl alcohol (1.0 g, 3.7 mmol) and THF (2.5 ml). A solution of 1 (0.047 g, 2 mol%) in THF (0.5 ml) was added and the container was sealed and removed from the glovebox. The flask was attached to a Schlenk line and after three pump/refill cycles, under a positive pressure of argon, the Teflon plug was removed and replaced with a rubber septum. A needle was introduced into the flask and placed into the reaction solution. A slow bubble of 1-butene was introduced and the reaction was allowed to stir with bubbling 1-butene for 4 hours. The reaction was quenched with excess ethyl vinyl ether, and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, using a slow gradient of hexanes to 9% EtOAc in hexanes) provided 7 (0.27 g, 40% yield, 77% Z as determined by 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.29-5.45 (2H, m), 3.63 (2H, t, J = 6.6 Hz), 1.94-2.06 (4H, m), 1.56 (2H, p, J = 6.7 Hz), 1.29 (11H, m), 0.95 (3H, m); 13 C NMR (CDCl 3 ): δ 131.6, 129.3, 63.1, 32.8, 32.6, 29.8, 29.5, 29.4, 29.2, 29.1, 20.5, 14.4; HRMS (FAB): 184.1830, [C 12 H 24 O] + requires 184.1827. (Z)-Dodec-9-en-1-yl acetate (8) Acetic anhydride (0.17 ml, 1.8 mmol), then pyridine (90 μl, 1.1 mmol), were added sequentially to alcohol 7 (0.17 g, 0.93 mmol) in CH 2 Cl 2 (1.8 ml), and stirred at room temperature for 17 hours. The mixture was diluted with diethyl ether, washed with saturated aqueous NaHCO 3, then brine, dried with Na 2 SO 4, and concentrated. Flash chromatography of the residue (SiO 2, 5% EtOAc in hexanes) provided 8 (0.18 g, 87% yield, 74% Z as determined by 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.28-5.43 S3

(2H, m), 4.05 (2H, t, J = 6.8 Hz), 2.04 (7H, m), 1.61 (2H, td, J = 9.8, 8.7, 4.6 Hz), 1.29 (10H, m), 0.95 (3H, m); 13 C NMR (CDCl 3 ): δ 171.3, 131.6, 129.3, 64.7, 32.6, 29.8, 29.5, 29.3, 29.2, 28.7, 26.0, 21.1, 20.6, 14.5; HRMS (FAB): 227.2045, [C 14 H 26 O 2 +H] + requires 227.2006. (Z)-Tetradec-11-en-1-ol (9) According to the procedure for compound 7, 11-eicosenol (1.1 g, 3.7 mmol) and THF (3 ml) were reacted with 1 (0.047 g, 2 mol%) to provide 9 (0.37 g, 47% yield, 76% Z as determined by 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.29-5.45 (2H, m), 3.63 (2H, t, J = 6.6 Hz), 1.94-2.06 (4H, m), 1.56 (2H, dt, J = 13.5, 6.7 Hz), 1.27, (15H, m), 0.96 (3H, m); 13 C NMR (CDCl 3 ): δ 131.7, 129.5, 63.2, 33.0, 29.9, 29.7, 29.7, 29.7, 29.6, 29.4, 27.2, 25.9, 20.7, 14.6; HRMS (FAB): 212.2135, [C 14 H 28 O] + requires 212.2140. (Z)-Tetradec-11-en-1-yl acetate (10) Acetic anhydride (0.17 ml, 1.8 mmol), then pyridine (86 μl, 1.1 mmol), were added sequentially to alcohol 7 (0.19 g, 0.89 mmol) in CH 2 Cl 2 (1.8 ml), and stirred at room temperature for 12 hours. The mixture was diluted with diethyl ether, washed with saturated aqueous NaHCO 3, then brine, dried with Na 2 SO 4, and concentrated. Flash chromatography of the residue (SiO 2, 5% EtOAc in hexanes) provided 13 (0.19 g, 84% yield, 77% Z as determined by 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.29-5.43 (2H, m), 4.05 (2H, t, J = 6.8 Hz), 2.04 (7H, m), 1.61 (2H, m), 1.27 (14H, m), 0.95 (3H, m); 13 C NMR (CDCl 3 ): δ 171.4, 131.7, 129.4, 64.8, 32.7, 29.9, 29.7 (2C), 29.4 (2C), 28.7, 27.2, 26.1, 21.2, 20.7, 14.6; HRMS (FAB): 255.2324, [C 16 H 30 O 2 +H] + requires 255.2319. S4

(Z)-Dodec-8-en-1-ol (12) In a glovebox, a 20 ml vial was charged with 8-nonenol (0.58 g, 4.1 mmol), 1-pentene (4 ml), and THF (4 ml). A solution of 1 (0.026 g, 1 mol%) in THF (0.5 ml) was added, and the mixture was stirred in an open vial for 4 hours. The vial was removed from the glovebox, the reaction was quenched with excess ethyl vinyl ether, and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, using a gradient of hexanes to 20% EtOAc in hexanes) provided 15 (0.56 g, 73% yield, 86% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.36 (2H, m), 3.64 (2H, br t, J = 5.3 Hz), 2.01 (4H, m), 1.36 (2H, m), 1.28-1.40 (11H, m), 0.90 (3H, t, J = 7.4 Hz); 13 C NMR (CDCl 3 ): δ 130.0, 129.7, 63.1, 32.8, 29.3 (4C), 27.2, 25.7, 22.9, 13.8; HRMS (EI): 184.1805, [C 12 H 24 O] + requires 184.1827. (Z)-Dodec-8-en-1-yl acetate (13) By cross metathesis of nonenyl acetate: according to the procedure for compound 15, 8-nonenyl acetate (0.76 g, 4.1 mmol) and 1-pentene (4 ml) in THF (4 ml) were reacted with 1 (0.026 g, 1 mol%) to provide 17 (0.60 g, 65% yield, 85% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.36 (2H, m), 4.05 (2H, t, J = 6.8 Hz), 2.05 (3H, s), 2.01 (4H, m), 1.62 (2H, m), 1.27-1.41 (10H, m), 0.90 (3H, t, J = 7.4 Hz); 13 C NMR (CDCl 3 ): δ 171.2, 129.9, 129.8, 64.7, 29.7, 29.3, 29.2 (2C), 28.6, 27.2, 25.9, 22.9, 21.0, 13.8; HRMS (EI): 227.2021, [C 14 H 26 O+H] + requires 227.2011. By acetylation of compound 2: According to the procedure for compound 6, Ac 2 O (0.29 ml, 3.0 mmol), pyridine (0.14 ml, 1.8 mmol), and alcohol 15 (0.28 g, 1.5 mmol) were reacted to provide 17 (0.19 g, 90% yield, 86% Z as determined by 1 H-NMR) as a colourless oil. (9Z,12E)-Tetradeca-9,12-dien-1-ol (15) According to the procedure for compound 3, oleyl alcohol (1.0 g, 3.7 mmol) and 1,4-trans-hexadiene (4 ml) in THF (4 ml) were reacted with 1 (0.023 g, 1 mol%) to provide 11 (0.53 g, 68% yield, 88% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.32-5.49 (4H, m), 3.64 (2H, br t, J = 6.6 S5

Hz), 2.71 (2H, m), 2.03 (2H, m), 1.03 (3H, m), 1.56 (2H, m), 1.25-1.39 (11H, m); 13 C NMR (CDCl 3 ): δ 130.4, 129.6, 127.7, 125.1, 63.1, 32.8, 30.4, 29.6, 29.5, 29.4, 29.2, 27.1, 25.7, 17.9; HRMS (FAB): 209.1906, [C 14 H 26 O-H] + requires 209.1905. (9Z,12E)-Tetradeca-9,12-dien-1-yl acetate (16) Acetic anhydride (3.1 mmol, 0.29 ml), then pyridine (1.8 mmol, 0.14 ml), were added sequentially to alcohol 11 (1.5 mmol, 0.32 g) in CH 2 Cl 2 (3 ml), and stirred at room temperature for 18 hours. The mixture was diluted with diethyl ether, washed with saturated aqueous NaHCO 3, then brine, dried with Na 2 SO 4, and concentrated. Flash chromatography of the residue (SiO 2, 10% EtOAc in hexanes) provided 13 (0.34 g, 89% yield, 88% Z as determined by 1 H-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.31-5.49 (4H, m), 4.05 (2H, t, J = 6.8 Hz), 2.72 (2H, m), 2.05 (3H, s), 2.02 (2H, m), 1.65 (2H, m), 1.61 (2H, m), 1.24-1.38 (11H, m); 13 C NMR (CDCl 3 ): δ 171.3, 130.4, 129.6, 127.7, 125.1, 64.7, 30.4, 29.6, 29.4, 29.2 (2C), 28.6, 27.1, 25.9, 21.0, 17.9; HRMS (FAB): 251.2000, [C 16 H 28 O 2 -H] + requires 251.2011. (Z)-Hexadec-1-en-6-ol (18) A solution of tert-butyllithium (19 ml, 1.7 M in pentanes) was added dropwise to a -78 C solution of 5-iodopentene (3.0 g, 15 mmol) in Et 2 O (25 ml), which was subsequently warmed to room temperature over 1 hour. The solution was re-cooled to -78 C, and undecanal (2.4 ml, 12 mmol) was added dropwise. The solution was let to warm to room temperature, washed with saturated NaHCO 3 (aq.), then brine, dried with Na 2 SO 4, and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, 10% EtOAc in hexanes) yielded 18 (4.2 g, 74%) as a colourless solid; 1 H NMR (CDCl 3 ): δ 5.81 (1H, m), 5.01 (1H, m), 4.95 (1H, m), 3.60 (1H, m), 2.08 (2H, m), 1.37-1.58 (7H, m), 1.22-1.34 (16H, m), 0.88 (3H, t, J = 6.9 Hz); 13 C NMR (CDCl 3 ): δ 138.8, 114.6, 71.9, 37.5, 36.9, 33.8, 31.9, 29.7, 29.6 (3C), 29.35, 25.7, 24.9, 22.7, 14.1. S6

(Z)-Henicos-6-en-11-ol (19) According to the procedure for compound 15, compound 18 (1.0 g, 4.2 mmol) and 1-heptene (4 ml) in THF (4 ml) were reacted with 1 (0.015 g, 0.5 mol%) to provide 19 (0.91 g, 70% yield, 88% Z as determined by quantitative 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.36 (2H, m), 3.59 (1H, m), 2.03 (4H, m), 1.21-1.54 (29H, m), 0.88 (6H, m); 13 C NMR (CDCl 3 ): δ 130.4, 129.4, 71.9, 37.6, 37.1, 31.9, 31.6, 29.7 (2C), 29.6 (2C), 29.4 (2C), 27.2 (2C), 25.8, 25.7, 22.7, 22.6, 14.1 (2C); HRMS (FAB): 309.3162, [C 21 H 42 O-H] + requires 309.3157. (Z)-Henicos-6-en-11-one (20) According to the procedure for compound 6, DMSO (0.080 ml, 1.1 mmol), oxalyl chloride (0.060 ml, 0.67 mmol), alcohol 19 (0.19 g, 0.61 mmol), and Et 3 N (0.42 ml, 3.1 mmol) were reacted to yield 20 (0.17 g, 91% yield, 88% Z as determined by quantitative 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.39 (1H, m), 5.31 (1H, m), 2.39 (2H, t, J = 7.5 Hz), 2.38 (2H, t, J = 7.6 Hz), 2.04 (2H, m), 1.99 (2H, m), 1.63 (2H, m), 1.56 (2H, m), 1.20-1.37 (20H, m), 0.88 (6H, m); 13 C NMR (CDCl 3 ): δ 211.4, 131.0, 128.7, 42.9, 42.1, 31.9, 31.5, 29.6, 29.5, 29.4 (2C), 29.3 (2C), 23.9, 22.7, 22.6, 14.1 (2C); HRMS (FAB): 309.3148, [C 21 H 40 O+H] + requires 309.3157. (Z)-Pentadec-4-en-1-ol (21) In a glovebox, a 20 ml vial was charged with 4-pentenol (410 μl, 3.98 mmol), 1-dodecene (4.4 ml), and THF (2.7 ml). A solution of 1 (0.025 g, 1 mol%) in THF (0.5 ml) was added, and the mixture was stirred in an open vial for 6 hours at 35 C. The vial was removed from the glovebox, the reaction was quenched with excess ethyl vinyl ether, and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, using a gradient of hexanes to 8% EtOAc in hexanes) provided 21 (0.56 g, 62% yield, S7

84% Z as determined by 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 5.38 (2Η, m), 3.65 (2H, m), 1.95-2.14 (4Η, m), 1.63 (2H, m), 1.52 (1H, s), 1.25 (16H, m), 0.87 (3H, t, J = 6.9 Hz); 13 C NMR (100 Hz, CDCl 3 ):δ 131.0, 128.9, 62.8, 32.8, 32.1, 29.9, 29.8, 29.7 (2C), 29.5 (2C), 29.3, 23.7, 22.8, 14.2; HRMS (FAB): 227.2372, [C 15 H 30 O+H] + requires 227.2369. (Z)-Pentadecen-4-en-1-yl 4-methylbenzenesulfonate (22) A 10 ml round bottom flask was charged with 21 (0.48 g, 2.12 mmol), Et 3 N (590 μl, 4.24 mmol), 4- dimethylaminopyridine (0.03 g, 0.21 mmol), and CH 2 Cl 2 (5 ml) under an argon atmosphere. The solution was cooled to 0 C, and a solution of 4-toluenesulfonyl chloride (0.61 g, 3.18 mmol) in CH 2 Cl 2 (1 ml) was added drop wise. The mixture was stirred vigourously for 4 hours at room temperature. The reaction mixture was treated with saturated aqueous NaHCO 3 (10 ml). After stirring at room temperature for 20 minutes, ethyl acetate (20 ml) was added. The organic layer was separated and washed with water (3x100 ml) and brine (50 ml), and dried over MgSO 4. The solution was filtered and the solvent was removed in vacuo. Flash chromatography of the residue (SiO 2, using a gradient of 2:1 hexanes/ch 2 Cl 2 to 1:1 hexanes/ch 2 Cl 2 ) provided 22 (0.68 g, 84% yield, 84% Z as determined by 13 C-NMR) as a colourless oil; 1 H NMR (CDCl 3 ): δ 7.79 (2H, d, J=8.3 Hz), 7.33 (2H, d, J = 8.9 Hz), 5.19-5.40 (2H, m), 4.02 (2H, t, J = 6.4 Hz), 2.44 (3H, s), 1.91-2.08 (4H, m), 1.66-1.71 (2H, m), 1.25 (16H, m), 0.88 (3H, t, J = 7.0 Hz); 13 C NMR (100 Hz, CDCl 3 ): δ 144.8, 144.7, 133.3, 131.8, 129.9, 128.0, 127.8, 127.4, 70.2, 32.6, 32.0, 29.7 (2C), 29.6 (2C), 29.5, 29.4, 29.0, 27.3, 23.1, 22.8, 14.3; HRMS (FAB): 381.2477, [C 22 H 36 O 3 S+H] + requires 381.2458. cis-7,8-epoxy-2-methyloctadecane ((±)-24) A 10 ml vial was charged with 22 (0.62 g, 1.63 mmol) and THF (2.2 ml) under an argon atmosphere and cooled to 78 C. 2 M isobutylmagnesium bromide in Et 2 O (1.2 ml, 2.45 mmol) was added. Next, 0.1 M Li 2 CuCl 4 in THF (160 μl, 0.016 mmol) was added in one portion, and the reaction mixture was warmed to room temperature and allowed to stir overnight. An ice-cooled saturated aqueous NH 4 Cl solution (5 ml) was added and the solution was extracted with pentane (3x 5 ml). The pentane S8

extract was washed with water (10 ml) and brine (10 ml), dried over MgSO 4, and concentrated in vacuo. Flash chromatography of the reside (SiO 2, using hexanes) provided a colorless oil that was used in the next step without further purification. The crude product was taken up in CH 2 Cl 2 (12 ml) and cooled to 0 C. A solution of mcbpa (0.35 g, 2 mmol) in CH 2 Cl 2 (12 ml) was added slowly. The reaction was warmed to room temperature and stirred for 3.5 hours. A saturated aqueous NaHCO 3 solution (25 ml) was added and the organic layer was dried over MgSO 4, filtered, and concentrated in vacuo. Flash chromatography of the residue (SiO 2, using a gradient of 1% EtOAc in hexanes to 15% EtOAc in hexanes) provided (±)-24 (0.30 g, 65% yield, 83% cis-isomer as determined by 1 H NMR). 1 H NMR (CDCl 3 ): δ 2.90 (2H, p, J = 4.2 Hz), 1.49 (9H, m), 1.26 (16H, m), 1.14-1.2 (2H, m), 0.87 (9H, m); 13 C NMR (CDCl 3 ): δ 57.4, 57.4, 39.1, 32.2, 32.1, 29.8, 29.7, 29.6, 29.5, 28.0 (3C), 27.5, 27.4, 26.8, 26.5, 26.2, 22.8 (2C), 14.3. HRMS (FAB): 282.2922, [C 19 H 38 ] + requires 282.2923. General Procedure for Time Course Experiment According to the procedure for compound 3, oleyl alcohol (2.0 g, 7.4 mmol) and 1-hexene (8 ml) in THF (8 ml) were reacted in the presence of 1 (0.046 g, 1 mol%). Aliquots (1 ml) were taken at t = 0.25, 0.5, 0.75, 1, 1.5, 2, 3, 4, 5, 7, removed from the glovebox, and quenched with ethyl vinyl ether. Purification by passage through a SiO 2 plug (hexanes to CH 2 Cl 2 ) provided a mixture of oleyl alcohol, 9-decenol, and 3, which was analyzed by quantitative 13 C-NMR spectroscopy. S9

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-tetradec-9-en-1-ol (3) S10

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-tetradec-9-en-1-ol (3) S11

HSQC spectrum of (Z)-tetradec-9-en-1-ol (3) S12

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-hexadec-11-en-1-ol (5) S13

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-hexadec-11-en-1-ol (5) S14

HSQC spectrum of (Z)-hexadec-11-en-1-ol (5) S15

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-hexadec-11-enal (6) S16

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-hexadec-11-enal (6) S17

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-Dodec-9-en-1-ol (7) S18

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-Dodec-9-en-1-ol (7) S19

HSQC spectrum of (Z)-Dodec-9-en-1-ol (7) S20

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-Dodec-9-en-1-yl acetate (8) S21

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-Dodec-9-en-1-yl acetate (8) S22

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-Tetradec-11-en-1-ol (9) S23

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-Tetradec-11-en-1-ol (9) S24

HSQC spectrum of (Z)-Tetradec-11-en-1-ol (9) S25

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-Tetradec-11-en-1-yl acetate (10) S26

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-Tetradec-11-en-1-yl acetate (10) S27

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-dodec-8-en-1-ol (12) S28

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)- dodec-8-en-1-ol (12) S29

HSQC spectrum of (Z)-dodec-8-en-1-ol (12) S30

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-dodec-8-en-1-yl acetate (13) S31

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-dodec-8-en-1-yl acetate (13) S32

1 H NMR (CDCl 3, 500 MHz) spectrum of (9Z,12E)-tetradeca-9,12-dien-1-ol (15) S33

13 C NMR (CDCl 3, 125 MHz) spectrum of (9Z,12E)-tetradeca-9,12-dien-1-ol (15) S34

HSQC spectrum of (9Z,12E )-tetradeca-9,12-dien-1-ol (15) S35

COSY spectrum of (9Z,12E )-tetradeca-9,12-dien-1-ol (15) S36

\1 H NMR (CDCl 3, 500 MHz) spectrum of (9Z,12E )-tetradeca-9,12-dien-1-yl acetate (16) S37

13 C NMR (CDCl 3, 125 MHz) spectrum of (9Z,12E )-tetradeca-9,12-dien-1-yl acetate (16) S38

1 H NMR (CDCl 3, 500 MHz) spectrum of hexadec-1-en-6-ol (18) S39

13 C NMR (CDCl 3, 125 MHz) spectrum of hexadec-1-en-6-ol (18) S40

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-henicos-6-en-11-ol (19) S41

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-henicos-6-en-11-ol (19) S42

HSQC spectrum of (Z)-henicos-6-en-11-ol (19) S43

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-henicos-6-en-11-one (20) S44

13 C NMR (CDCl 3, 125 MHz) spectrum of (Z)-henicos-6-en-11-one (20) S45

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-Pentadec-4-en-1-ol (21) S46

13 C NMR (CDCl 3, 100 MHz) spectrum of (Z)-Pentadec-4-en-1-ol (21) S47

HSQC spectrum of (Z)-Pentadec-4-en-1-ol (21) S48

1 H NMR (CDCl 3, 500 MHz) spectrum of (Z)-Pentadecen-4-en-1-yl 4-methylbenzenesulfonate (22) S49

13 C NMR (CDCl 3, 100 MHz) spectrum of (Z)-Pentadecen-4-en-1-yl 4-methylbenzenesulfonate (22) S50

1 H NMR (CDCl 3, 500 MHz) spectrum of cis-7,8-epoxy-2-methyloctadecane (±)-24 S51

13 C NMR (CDCl 3, 125 MHz) spectrum of cis-7,8-epoxy-2-methyloctadecane (±)-24 S52

HSQC spectrum of cis-7,8-epoxy-2-methyloctadecane (±)-24 S53