Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
Hydrolytic kinetic resolution of mono- and bisepoxides as a key step in
the synthesis of insect pheromones
Sharon Chow and William Kitching*
Department of Chemistry, The University of Queensland, Brisbane, 4072, Australia.
kitching@chemistry.uq.edu.au
1.
2.
3.
Illustrative procedure for HKR of a bisepoxide;
Comparison of Sharpless asymmetric dihydroxylation and HKR;
Listing of key references for insect pheromones in the report.
1.
HKR of bisepoxide of 1,8-nonadiene
H
E-mail:
H
N
H2O
N
Co
But
O
t
O
OAc
t
Bu
But
Bu
(R,R)-1
Bisepoxide 19 (1.37g, 8.78mmol) was stirred with (R,R)-1 (76mg, 107mol) and H2O (120L, 6.67mmol)
at room temperature for 21 hours. The resulting mixture was separated by flash chromatography on silica
to yield bisepoxide 20 (24%), epoxydiol 21 (46%) and tetrol 22 (15%).
Bisepoxide 20: 1H NMR (400MHz, CDCl3) - 2.88 (2H, m), 2.72 (2H, dd, J = 5.00 & 4.00Hz), 2.44 (2H,
dd, J = 5.04 & 2.76Hz), 1.47 (10H, m); 13C NMR (100MHz, CDCl3) - 52.3, 47.0, 32.3, 29.2, 25.8;
[]D23 +20.68o (c 1.03, CHCl3). Lit value []D +20.43o (S. Takano, Y, Shimazaki, M. Takahashi and K.
Ogasawara, J. Chem. Soc., Chem. Commun, 1988, 1004.)
For the ease of analyses, epoxydiol 21 and tetrol 22 were converted to the corresponding epoxyacetonide
and bisacetonide, by the treatment with excess of 2,2-dimethoxypropane in DCM and a catalytic amount of
tosic acid.
Epoxyacetonide from 21: 1H NMR (400MHz, CDCl3) - 4.03 (1H, m), 3.99 (1H, t, J = 7.44Hz), 3.46
(1H, t, J = 7.16Hz), 2.86 (1H, m), 2.71 (1H, dd, J = 5.00 & 4.00Hz), 2.42 (1H, dd, J = 5.04 & 2.27Hz),
1.26-1.61 (10H, m), 1.37 (3H, d, J = 0.40Hz), 1.32 (3H, d, J = 0.48Hz); 13C NMR (100MHz, CDCl3) 106.8, 76.0, 69.5, 52.3, 47.0, 33.5, 32.3, 29.4, 26.9, 25.8, 25.70, 25.66; []D23 +21.90o (c
1.15, CHCl3).
Bisacetonide from 22: 1H NMR (400MHz, CDCl3) - 4.03 (2H, m), 3.98 (2H, t, J = 7.40Hz), 3.45 (2H, t,
J = 7.16Hz), 1.24-1.60 (10H, m), 1.36 (3H, d, J = 0.40Hz), 1.30 (3H, d, J = 0.48Hz); 13C NMR
(100MHz, CDCl3) - 108.6, 76.0, 69.4, 33.5, 29.6, 26.9, 25.7, 25.6; []D23 +24.51o (c 1.05,
CHCl3).
2.
Comparison of Sharpless asymmetric dihydroxylation and HKR of the benzyl ether of 10-undecenol
For comparison purposes, we conducted Sharpless asymmetric dihydroxylation of benzyl ether 2 with ADmix, and the derived acetonide exhibited []D23 +9.60o (c 1.07, CHCl3), whereas the acetonide of 5 had
[]D23 +10.60o (c 1.04, CHCl3). These and other data correspond to an ee of 81% in the AD-reaction and in
excess of 90% for the HKR.
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
3.
Listing of key references for insect pheromones synthesised in the report.
(R)-(-)-10-methyldodecyl acetate 8 from the smaller tea tortrix moth (Adoxophyes species)
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 C.H. Nguyen, M.V. Mavrov and E.P. Serebryakow, Izv. Akad. Nauk SSSR, Ser. Khim., 1988, 690.
(R)-(-)-10-Methyl-2-tridecanone 12 from the southern corn rootworm (Diabrotica undecimpunctata)
 P.E. Sonnet, J. Org. Chem., 1982, 47, 3793.+
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(R)-(-)-(Z)-6-Undecen-2-ol 18 (Nostrenol) from ant-lions (Euroleon nostras and Grocus bore)
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(1R,7R)-1,7-Dimethylnonyl propanoate 26 from the female western corn rootworm (Diabrotica virgifera
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 E. Keinan, S.C. Sinha and A. Sinha-Bagchi, J. Org. Chem., 1992, 57, 3631.
(6R,12R)-6,12-Dimethyl-2-pentadecanone 29 from the female banded cucumber beetle (Diabrotica
balteata)
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 D. Enders, B. Jandeleit and O.F. Prokopenko, Tetrahedron, 1995, 51, 6273.+
(2S,11S)-2,11-Diacetoxytridecane 35 from female pea midge (Contarinia pisi)
 Y. Hillbur, P. Anderson, H. Arn, M. Bengtsson, J. Lfqvist, A.J. Biddle, O. Smitt, H.-E. Hgberg, E.
Plass, S. Francke and W. Francke, Naturwissenschaften, 1999, 86, 292.+
7,11-Dimethylheptadecane 39 from the spring hemlock looper (Lambdina athasaria)
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15,19-Dimethyltritriacontane 40 from female stable flies (Stomoxys calcitrans)
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(4R,8R)-4,8-Dimethyldecanal 41 (Tribolure) from several Tribolure species
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