A. Darwish, J.M. Chong / Tetrahedron 68 (2012) 654e658
657
1.56e1.28 (m, 9H), 0.87 (t, 3H, J¼6.2 Hz); 13C NMR (75 MHz, CDCl3)
1.0 mmol), and CuI (0.38 g, 2.0 mmol). Hexyne (11.7 mL, 0.100 mol)
was then added and the reaction mixture was stirred vigorously (to
ensure the two phase system was emulsified) for 24 h. The reaction
mixture was diluted with hexane. The layers were separated, and
the aqueous layer was extracted with hexane (2ꢂ150 mL). The or-
ganic layers were combined and washed with saturated NH4Cl
(3ꢂ100 mL), brine (2ꢂ100 mL), dried over Na2SO4, and concen-
trated. The resulting oil was purified by silica gel (600 g) chroma-
tography (hexane/ether, 25:1) to afford enyne 7 (11.7 g, 82% yield)
d
148.6, 77.1, 74.7, 36.5, 31.6, 24.7, 22.5, 13.9.
4.2.9. (E)-3-Iodo-1-phenylprop-2-en-1-ol (2i)39. Vinyl iodide 2i was
isolated in 80% yield from a 82:18 mixture of 2i and 3i formed from
alkyne 1i using the general procedure. 1H NMR (300 MHz, CDCl3)
d
7.39e7.30 (m, 5H), 6.70 (dd, 1H, J¼14.4, 5.9 Hz), 6.45 (dd, 1H,
J¼14.5, 1.1 Hz), 5.13 (m, 1H), 2.21 (d, 1H, J¼3.4 Hz); 13C NMR
(75 MHz, CDCl3)
76.6.
d 147.1, 141.9, 128.7 (2C), 128.2, 126.3 (2C), 78.1,
as a colorless oil. 1H NMR (300 MHz, CDCl3)
d
5.96 (dt, 1H, J¼15.8,
7.0 Hz), 5.37 (d, 1H, J¼15.0 Hz), 3.98 (t, 2H, J¼6.7 Hz), 2.20 (dt, 2H,
J¼7.2, 1.9 Hz), 2.01 (s, 3H), 2.00 (app q, 2H, J¼7.3 Hz), 1.55e1.23 (m,
12H), 1.15e1.06 (m, 4H), 0.85 (t, 3H, J¼7.1 Hz); 13C NMR (75 MHz,
4.2.10. (E)-Hexadec-9-en-11-yn-1-ol (4)40. To a mixture of iodides
2b and 3b (95:5, 130 mg, 0.46 mmol), Pd(PPh3)2Cl2 (32.0 mg,
0.046 mmol) and CuI (18.0 mg, 0.093 mmol) in Et3N (10 mL) was
added a dilute solution of hexyne (76.0 mg, 0.93 mmol) in Et3N
(2 mL) at rt. The reaction was allowed to stir at rt for 16 h. The re-
action mixture was diluted with water (25 mL) and the aqueous
layer was extracted with ether (2ꢂ25 mL). The organic layers were
combined and washed with saturated NH4Cl (2ꢂ30 mL) and brine
(2ꢂ30 mL), then dried over Na2SO4 and concentrated. The resulting
oil was purified by silica gel (7 g) chromatography (hexane/ether,
3:1) to afford enyne 4 in 85% (92 mg) yield as a colorless oil. 1H NMR
CDCl3)
d 171.0, 143.0, 109.8, 88.5, 79.0, 64.5, 32.8, 30.8, 29.2, 29.1,
28.9, 28.7, 28.5, 25.8, 21.9, 20.9, 18.9, 13.5.
4.2.14. (9E,11Z)-Hexadeca-9,11-dien-1-yl acetate (8)30b. To a solu-
tion of 2-methyl-2-butene (20.8 mL, 195 mmol) in THF (65 mL) at
0
ꢀC was added BH3ꢃSMe2 (9.70 mL, 97.0 mmol). After 20 min, the
disiamylborane was syringed, dropwise, into a solution of enyne 7
(17.5 g, 65.0 mmol) in THF (65 mL) at 0 ꢀC over a period of 30 min.
The mixture was allowed to stir at 0 ꢀC for 4 h. AcOH (22 mL,
0.39 mol) was added slowly and the reaction was stirred at 55 ꢀC for
6 h then allowed to cool to rt. This was followed by the addition of
NaOH (82 mL, 25% w/v in H2O) and H2O2 (22 mL, 30% in H2O) and
stirring for 30 min at 40 ꢀC. The mixture was cooled, diluted with
ether (200 mL), washed with brine (2ꢂ100 mL), dried over Na2SO4
and concentrated. The resulting oil was purified by silica gel (600 g)
chromatography (hexane/ether, 30:1) to afford diene 8 (12.20 g,
(300 MHz, CDCl3)
d
6.02 (dt, 1H, J¼15.8, 7.2 Hz), 5.42 (d, 1H,
J¼16.0 Hz), 3.61 (t, 2H, J¼6.3 Hz), 2.27 (dt, 2H, J¼7.2, 1.9 Hz), 2.03
(app q, 2H, J¼7.3 Hz), 1.53e1.16 (m, 12H) (m, 4H), 0.89 (t, 3H,
J¼7.2 Hz); 13C NMR (75 MHz, CDCl3)
d 143.0, 109.7, 88.5, 79.0, 63.7
(CH2OH), 32.8, 32.6, 30.8, 29.3, 29.2, 28.9, 28.7, 25.6, 21.8, 18.9, 13.5.
4.2.11. (9E,11Z)-Hexadeca-9,11-dien-1-ol (5)27. To a solution of 2-
methyl-2-butene (0.15 mL, 1.44 mmol) in THF (5 mL) at 0 ꢀC was
added BH3ꢃSMe2 (0.07 mL, 0.72 mmol). After 20 min, a solution of
enyne 4 (85 mg, 0.36 mmol) in THF (1 mL) was added dropwise and
the mixture was allowed to stir at 0 ꢀC for 4 h. AcOH (0.16 mL,
2.9 mmol) was added slowly and the reaction was stirred at 55 ꢀC
for 6 h then allowed to cool to rt. This was followed by the addition
of NaOH (0.29 mL, 50% w/v in H2O) and H2O2 (0.16 mL, 30% in H2O)
and stirring for 30 min at 40 ꢀC. The mixture was cooled, diluted
with ether (30 mL), washed with brine (2ꢂ30 mL), dried over
Na2SO4 and concentrated. The resulting oil was purified by silica gel
(10 g) chromatography (hexane/ether, 3:1) to afford diene 5
(81 mg, 94% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3)
70% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3)
d 6.13 (dd,
1H, J¼14.7, 11.3 Hz), 5.76 (dd, 1H, J¼10.8 Hz), 5.46 (dt, 1H, J¼15.0,
7.0 Hz), 5.11 (dt, 1H, J¼10.5, 7.7 Hz), 3.88 (t, 2H, J¼6.7 Hz), 2.01e1.90
(m, 4H), 1.84 (s, 3H), 1.62e1.16 (m, 16H), 0.75 (t, 3H, J¼6.7 Hz); 13C
NMR (75 MHz, CDCl3)
d 170.3, 133.9, 129.4, 128.6, 125.6, 64.1, 32.7,
31.7, 29.2 (2C), 29.0, 28.9, 28.5, 27.2, 25.7, 22.1, 20.5, 13.7.
Acknowledgements
We thank the Natural Sciences and Engineering Research
Council of Canada (NSERC) for financial support.
d
6.27 (dd,1H, J¼14.6, 11.4 Hz), 5.90 (dd, 1H, J¼10.8 Hz), 5.60 (dt, 1H,
J¼15.0, 6.9 Hz), 5.25 (dt, 1H, J¼10.4, 7.7 Hz), 3.58 (t, 2H, J¼6.6 Hz),
2.14e2.01 (m, 4H), 1.92 (s, 1H), 1.52e1.22 (m, 16H), 0.87 (t, 3H,
References and notes
J¼6.7 Hz); 13C NMR (75 MHz, CDCl3)
d 134.5, 130.0, 128.5, 125.6,
€
1. Hegedus, L. S.; Soderberg, B. C. G. Transition Metals in the Synthesis of Complex
62.8, 32.8, 32.7, 31.8, 29.4, 29.3 (2C), 29.1, 27.3, 25.7, 22.2, 13.7.
Organic Molecules, 3rd ed.; University Science: Sausalito, CA, 2009.
2. (a) Farina, V.; Krisnamurthy, V.; Scott, W. J. Org. React. 1997, 50, 1e652; (b)
Espinet, P.; Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 4704e4734; (c)
4.2.12. (9E,11Z)-Hexadeca-9,11-dienal (6)27. A solution of alcohol 5
€
Furster, A.; Funel, J.-A.; Tremblay, M.; Bouchez, L. C.; Nevado, C.; Waser, M.;
(81 mg, 0.34 mmol) in CH2Cl2 (1 mL) was added dropwise to
Ackerstaff, J.; Stimson, C. C. Chem. Commun. 2008, 2873e2875; (d) Gallagher,
W. P.; Maleczka, R. E., Jr. J. Org. Chem. 2005, 70, 841e846.
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C.; Liebeskind, L. S. Org. Lett. 2001, 3, 2149e2152; (c) Mori, Y.; Nakamura, M.;
Wakabayashi, T.; Mori, K.; Kobayashi, S. Synlett 2002, 601e603.
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Chen, C. Tetrahedron Lett. 2008, 49, 2916e2921.
ꢀ
a mixture of PDC (192 mg, 0.51 mmol) and 3 A sieves (100 mg) in
CH2Cl2 (10 mL) and the mixture was stirred at rt for 18 h. The re-
action mixture was diluted with ether, passed through a Celite plug
and concentrated. The resulting oil was purified by silica gel chro-
matography (10 g, hexane/ether, 15:1) to afford aldehyde 6 (73 mg,
5. (a) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135e631; (b) Marquais, S.;
Cahiez, G.; Knochel, P. Synlett 1994, 849e850.
91% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3)
d 9.74 (s, 1H),
6.28 (dd, 1H, J¼14.3, 11.7 Hz), 5.91 (dd, 1H, J¼10.8, 10.8 Hz), 5.62 (dt,
1H, J¼15.0, 6.9 Hz), 5.27 (dt, 1H, J¼10.2, 7.7 Hz), 2.39 (t, 2H,
J¼7.3 Hz), 2.14e2.09 (m, 2H), 1.62e1.16 (m, 18H), 0.88 (t, 3H,
6. Kakusawa, N.; Yamaguchi, K.; Kurita, J. J. Organomet. Chem. 2005, 690,
2956e2966.
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1959e1966.
J¼6.5 Hz); 13C NMR (75 MHz, CDCl3)
d 202.4, 134.2, 129.9, 128.5,
ꢁ
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125.6, 43.0, 32.7, 31.7, 29.2 (2C), 32.7, 31.8, 29.2, 29.1, 29.0, 28.9, 27.3,
22.2, 21.9, 13.8.
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4.2.13. (E)-Hexadec-9-en-11-ynyl acetate (7)40. To a degassed mix-
ture of aqueous 10% NaOH (100 mL) and benzene (55 mL) was
added successively iodides 2c and 3c (95:5 ratio, 16.54 g,
51.0 mmol), BnNEt3Cl (0.23 g, 1.0 mmol), Pd(PPh3)4 (1.1 g,