H
A. Lehr et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3, COSY): = 7.09 (t, 3JHH = 7.8 Hz, 1 H, H-31),
5.29–5.19 (br m, 1 H, H-2), 4.58–4.40 (br m, 2 H, H-5), 4.38 (br d, 2JHH
= 11.8 Hz, 1 H, H-1a), 4.21–4.01 (br m, 3 H, H-1b, H-3), 3.96–3.71 (br
m, 2 H, H-4), 3.32 (br s, 9 H, H-6), 2.58 (br t, 3JHH = 7.4 Hz, 2 H, H-33),
(8) Melo, T.; Marques, S. S.; Ferreira, I.; Cruz, M. T.; Domingues, P.;
Segundo, M. A.; Domingues, M. R. M. Lipids 2018, 53, 117.
(9) (a) Bittmannn, R. In Phospholipids Handbook; Cevc, G., Ed.;
Marcel Dekker: New York, 1995, 141–232. (b) D’Arrigo, P.; Servi,
S. Molecules 2010, 15, 1354. (c) Xia, J.; Hui, Y. Z. Tetrahedron:
Asymmetry 1997, 8, 451.
2.38–2.28 (m, 4 H, H-8, H-24), 2.24 (q, 3JHH, = 7.5 Hz, H-30), 1.66–1.55
3
(m, 4 H), 1.54–1.45 (m, 4 H), 1.38–1.23 (m, 40 H), 0.90 (2×br t, JHH
=
6.5 Hz, 6 H, H-22, H-40).
(10) (a) Choi, J.; Laird, J. M.; Salomon, R. G. Bioorg. Med. Chem. 2011,
19, 580. (b) Acharya, H. P.; Kobayashi, Y. Synlett 2005, 2015.
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Salomon, R. G. J. Org. Chem. 2003, 68, 3749. (c) Picq, M.; Han, Y.;
Lagarde, M.; Doutheau, A.; Nemoz, G. J. Med. Chem. 2002, 45,
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Radical Biol. Med. 2013, 59, 14. (b) Woodcock, S. R.; Salvatore, S.
R.; Bonacci, G.; Schopfer, F. J.; Freeman, B. A. J. Org. Chem. 2014,
79, 25. (c) Lim, D. G.; Sweeney, S.; Bloodsworth, A.; White, C. R.;
Chumley, P. H.; Krishna, N. R.; Schopfer, F. J.; O’Donnell, V. B.;
Eiserich, J. P.; Freeman, B. A. Proc. Natl. Acad. Sci. U.S.A. 2002, 99,
15941. (d) O’Donnell, V. B.; Eiserich, J. P.; Bloodsworth, A.;
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(14) The stereoselective nitration of olefins with AgNO2 and TEMPO
developed by Maiti and co-workers was tested. Such an adapted
reaction starting from oleic acid delivered a 3:3:1:1 mixture of
(E)-9-nitro 4 and (E)-10-nitrooleic acid 5 as well as the corre-
sponding Z isomers as minor products. Laborious HPLC pro-
cesses were necessary do separate the E isomers (small scale).
For more detailed information, see the Supporting Information:
Maity S., Manna S., Rana S., Naveen T., Mallick A., Maiti D.; J. Am.
Chem. Soc.; 2013, 135: 3355
13C NMR (100 MHz, CDCl3, HSQC): = 173.59 (C-7), 173.10 (C-23),
151.95 (C-32), 136.31 (C-31), 69.96 (C-2), 66.55 (C-4), 64.26 (C-3),
62.40 (C-1), 59.85 (C-5), 54.72 (C-6), 34.11 (C-8/24), 34.06 (C-8/24),
31.94 (C-20/38), 31.82 (C-20/38), 29.71 (3×C), 29.67 (2×C), 29.54,
29.38, 29.34, 29.25 (2×C), 29.17 (2×C), 29.09, 29.03, 28.86, 28.46,
27.97 (2×C, C-30/34), 27.92 (C-30/34), 26.37 (C-33), 24.87, 24.74,
22.71 (C-21/39), 22.65 (C-21/39), 14.14 (C-22/C40), 14.10 (C-22/C-
40).
HRMS ESI: m/z [M + H]+ calcd for C42H82N2O10P: 805.5702; found:
805.5711; m/z [M + Na]+ calcd for C42H81N2O10P23Na: 827.5521;
found: 827.5525.
Acknowledgment
We are grateful to Dr. Stefan Heckhoff, Corden Pharma Switzerland
LLC for 1-palmitoyl-2-lyso-sn-glycero-3-phosphatidylcholine.
Supporting Information
Supporting information for this article is available online at
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J