8878
E. Vaique et al. / Tetrahedron 66 (2010) 8872e8879
(ESIþ) 463.5 ([MþNa]þ, 100%); HRMS (ESIþ) calcd for C28H40O4Na
2-monoacylglycerols and free fatty acids were subjected to gas
chromatography.
463.2824 found 463.2820.
Acknowledgements
4.3. General procedure to access to structured triacylglycerols
This work was supported by the French Ministry of Research,
the Centre National de Recherche Scientifique and Région Aqui-
taine. We thank Mr. N. Pinaud for his contribution in NOESY
experiments.
To a mixture of 4 or 5 (1 equiv) and fatty acid (4 equiv) in an-
hydrous CH2Cl2 (3 mL/mmol) at 0 ꢀC was added slowly TFAA
(4 equiv). At the end of the addition, the resulting brown solution
was stirred at room temperature for 3 days. The solvent was
evaporated in vacuo and the crude residue purified by silica gel
chromatography (5% AcOEt/hexane) to give pure triacylglycerol 6
or 7.
Supplementary data
All compounds 6 and 7 were prepared according to this pro-
cedure. Compounds 6a and 7a are given as examples. Details con-
cerning the synthesis and the characterization data of other
structured triacylglycerols are given in the Supplementary data.
Optimization of the acylation, kinetics studies of the 1:2 mixture
acylation, detailed experimental procedures, characterization of
products 4a, 4ced, 5a, 5ced, 6bef, 7bef and NMR spectra of all
compounds are reported. Supplementary data associated with this
the most important compounds described in this article.
4.3.1. Octadeca-9,12,15-trienoic acid 2-heptadecanoyloxy-1-hepta-
decanoyloxymethyl-ethyl ester 6a. Compound 6a was prepared from
4b (306 mg, 0.695mmol) and heptadecanoic acid(712 mg, 2.78mmol)
in 48% yield (285 mg, 0.33 mmol) as colourless oil; [Found: C, 76.77; H,
11.47. C55H100O6 requires C, 77.05; H 11.76%]; Rf (20% AcOEt/hexane)
References and notes
0.78; nmax (KBr) 2921, 2851,1743,1466,1253,1165,1098 and 717 cmꢂ1
;
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dH (400 MHz; CDCl3; Me4Si) 5.45e5.26 (7H, m), 4.29 (2H, dd, J¼11.9
and 4.3), 4.14 (2H, dd, J¼11.9 and 5.9), 2.82e2.79 (4H, m), 2.40e2.25
(6H, m), 2.12e2.01 (4H, m),1.67e1.55(6H, m),1.45e1.15 (60H, m), 0.97
(3H, t, J¼7.6) and 0.88 (6H, t, J¼7.2); dC (100 MHz, CDCl3, Me4Si) 173.3,
172.8, 131.9, 130.2, 128.3, 128.2, 127.8, 127.1, 68.9, 62.1, 34.2, 34.0, 31.9,
29.71, 29.68, 29.64, 29.62, 29.5, 29.4, 29.3, 29.2, 29.1, 29.0, 27.2, 25.6,
25.5, 24.9, 22.7, 20.6, 14.3 and 14.1.
4.3.2. Octadeca-9,12,15-trienoic acid 2,3-bis-heptadecanoyloxy-pro-
pyl ester 7a. Compound 7a was prepared from 5b (205 mg,
0.465 mmol) and heptadecanoic acid (477 mg, 1.86 mmol) in 68%
yield (272 mg, 0.32 mmol) as colourless oil; Rf (20% AcOEt/hexane)
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€
8. (a) Christensen, M. S.; Hoy, C.-E.; Becker, C. C.; Redgrave, T. G. Am. J. Clin. Nutr.
dH (400 MHz; CDCl3; Me4Si) 5.44e5.23 (7H m), 4.29 (2H, dd,
J¼11.9 and 4.3), 4.14 (2H, dd, J¼11.9 and 6.0), 2.85e2.75 (4H, m),
2.38e2.27 (6H, m), 2.13e2.02 (4H, m), 1.68e1.53 (6H, m), 1.45e1.2
(60H, m), 0.97 (3H, t, J¼7.6) and 0.88 (6H, t, J¼7.2); dC (100 MHz,
CDCl3, Me4Si) 173.3, 173.2, 172.9, 132.0, 130.2, 128.3, 128.2, 127.8,
127.1, 68.9, 62.1, 34.2, 34.1, 34.0, 31.9, 29.72, 29.68, 29.64, 29.61,
29.52, 29.50, 29.4, 29.31, 29.29, 29.2, 29.14, 29.10, 27.2, 25.6, 25.5,
24.93, 24.89, 24.85, 22.7, 20.6, 14.3 and 14.2; m/z (ESIþ) 879
([MþNa]þ, 100%); HRMS (ESIþ) calcd for C55H100O6Na 879.7412
found 879.7398.
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The intramolecular fatty acid distribution in TGs was de-
termined according to a method described with slight modifica-
tions.19 Briefly, lipase-catalyzed hydrolysis experiments were
performed in a thermostated bath at 40 ꢀC and pH 8. The reaction
mixture consisted of 15 mg of TGs, 1 g of porcine pancreatin sus-
pended in 1 mL of TriseHCl buffer (1.0 M adjusted to a pH of 8.0),
0.2 mL of aqueous solution of calcium chloride (22%; wt/vol) and
0.5 mL of aqueous solution of sodium deoxycholate (0.1%; wt/vol).
The resulting 2-monoacylglycerols and free fatty acids were sepa-
rated by thin layer chromatography (TLC). TLC was performed with
Merck silica gel (60H) spread on 20ꢁ20 cm glass plates, 0.35 mm
thick, activated at 110 ꢀC for 1 h hexane/diethyl ether/formic acid
(70/30/1, vol/vol/vol) was used as developing solvent. Respective
fractions were transmethylated in the presence of boron tri-
fluoride/methanol complex.21 Fatty acid methyl ester (FAME) of