4
Reduction of the propargyl alcohol, 19, was carried
2. Moore, J. E. Tropical Pest Management 1983, 29,
1
9
231-238.
out with LiAlH4 to obtain the corresponding E-
allylic alcohol 20, which was acetylated with acetic
anhydride without any further purification. Allylic
acetate, 21, was purified by high vacuum distillation
and isolated in 72% overall yield from 19.
3
.
Filho, M. M.; Vilela, E. F.; Jham, G. N.; Attygalle,
A.; Svatos, A.; Meinwald, J. J. Braz. Chem. Soc.
000, 11, 621-628.
2
4. Cabello, T.; Gallego, J.R.; Vila, E.; Soler, A.; del
Pino, M.; Carnero, A.; Hernández-Suárez, E.;
Polaszek, A. Integrated Control Protected Crops.
Mediterranean Climate. IOBC/wprs Bulletin 2009,
49, 225-230.
2
0
Bromide 23, easily prepared from commercially
available (3Z,6Z)-3,6-nonadien-1-ol, 22, was treated
with magnesium in ether, to form the corresponding
5
.
Desneux, N.; Wajnberg, E.; Wyckhuys, K. A. G.;
Burgio, G.; Arpaia, S.; Narváez-Vásquez, C. A.;
González-Cabrera, J.; Ruescas, D. C.; Tabone, E.;
Frandon, J.; Pizzol, J.; Poncet, C.; Cabello, T.;
Urbaneja, A. J. Pest. Sci. 2010, 83, 197-215.
2
1
Grignard reagent. A titration of an aliquot revealed
that the reagent was formed in 65% yield. This
Grignard was coupled with 0.91 equivalents of
allylic acetate 21, assisted by catalytic amounts of
lithium tetrachlorocuprate, Li CuCl . The crude
6. Guenaoui, Y. Phytoma-La Défense des Végétaux
008, 617, 18-19.
2
7
8
9
.
.
.
El-Aassar, M. R.; Soliman, M.H.A.; Abd Elaal,
A.A. Ann. Agric. Sci. 2015, 60, 153-156.
Desneux, N.; Luna, M. G.; Guillermaud, T.;
Urbaneja, A. J. Pest. Sci. 2011, 84, 403-408.
Canadian Food Inspection Agency. Tuta absoluta
2
4
reaction was purified by column chromatography to
obtain triene, 16, in 90% isolated yield.
Deprotection of 16, was performed under very mild
conditions, with PPTS in ethanol 95%, at 60 C for
o
4
8 hours. Alcohol 11, was purified by column
1
0. Food and agriculture Organization of the United
Nations.
www.fao.org/news/story/en/item/152712/icode/
11. Urbaneja, A.; Montón, H.; Mollá, O. J. Appl.
Entomol. 2009, 133, 292-296.
chromatography and obtained in 88% yield.
Acetylation of 11 was accomplished using acetic
anhydride,
triethylamine
and
4-
dimethylaminopyridine as
a catalyst to obtain
1
2. Food and Agriculture Organization of the United
Nations 2017, 1, 1-20.
acetate, 1, in 98% yield.
1
3. Attygalle, A. B.; Jham, G. N.; Svatos, A.; Frighetto,
R.T.S.; Meinwald, J.; Vilela, E.F.; Ferrara, F.A.;
Uchoa-Fernandes, M.A. Tetrahedron Lett. 1995,
36, 5471-5474.
4. Attygale, A. B., Jham, G.N.; Svatos, A.; Frighetto,
R.T.S; Ferrara, F.A.; Vilela, E.F.; Uchoa-
Fernandes, M.A.; Meinwald, J. Bioorg. Med.
Chem. 1996, 4, 305-314
In summary, a new and efficient synthesis of the
major pheromone component of the tomato
leafminer moth, Tuta absoluta, was developed. The
final product, 1, was obtained with an overall yield
of 41% from but-3-yn-1-ol, 17. To date, this is the
highest overall percent yield reported for the
synthesis of this pheromone. When compared to
previous syntheses, the key C5-C6 bond formation in
this new synthetic scheme strategically enabled the
use of the readily accessible 9-carbon bromide 23,
greatly streamlining and effectively removing
synthetic and purification steps leading to acetate, 1.
This is the first reported synthesis that has been
scaled-up to obtain 15 grams of pheromone 1, per
batch, which allows its broad use in the field.
1
1
5. Griepink, F.C.; van Beek, T. A.; Posthumus, M. A.;
de Groot, A. Tetrahedron Lett. 1996, 37, 411-414.
16. Svatos, A.; Attygalle, A. B.; Jham, G. N.; Frighetto,
R. T. S.; Vilela, E. F.; Saman, D.; Meinwald, J. J.
Chem. Ecol. 1996, 22, 787-800.
1
7. Ferrara, F. A. A.; Vilela, E. F.; Jham, G. N.; Eiras,
A. E.; Picanco, M. C.; Attygalle, A. B.; Svatos, A.;
Frighetto, R. T. S.; Meinwald, J. J. Chem. Ecol.
2001, 27, 907-916
1
1
2
2
8. Puigmartí, M.; Bosch, M. P.; Guerrero, A. Synthesis
2
015, 47, 961-968.
9. Corey, E. J.; Katzenellenbogen, J. A.; Posner, G. H.
J. Am. Chem. Soc. 1967, 89, 4245-4247.
0. Chun, J.; Li, G.; Byun, H.-S.; Bittman, R. J. Org.
Chem. 2002, 67, 2600. ꢀ
Acknowledgments
1. Waston, S.C.; Eastham, J.F. J. Organomet. Chem.
Professor Jürgen Anthony of UCR is gratefully
acknowledged for his assistance in the recording of
NMR spectra. Lorena Hernández of Ciprona-UCR is
acknowledged for recording the high-resolution mass
spectra, and Vicerrectoría de Investigación (UCR) is
acknowledged for financial support.
1
967, 9, 165.
Supplementary Material
Detailed synthetic procedures and NMR spectra are
provided.
References and notes
1
.
Cisneros, F. H. Rev. Per. De Em. 1966, 9, 101-106.