7212
J. R. Falck et al. / Tetrahedron Letters 42 (2001) 7211–7212
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Hammock, B. D.; Snapper, J. R.; Capdevila, J. H. J.
Biol. Chem. 1993, 268, 6402–6407.
8. Karara, A.; Dishman, E.; Falck, J. R.; Capdevila, J. H. J.
Biol. Chem. 1991, 266, 7561–7569.
9. Spearman, M. E.; Prough, R. A.; Estabrook, R. W.;
Falck, J. R.; Manna, S.; Leibman, K. C.; Murphy, R. C.;
Capdevila, J. H. Arch. Biochem. Biophys. 1985, 242,
225–230.
10. Carroll, M. A.; Balazy, M.; Margiotta, P.; Falck, J. R.;
McGiff, J. C. J. Biol. Chem. 1993, 268, 12260–12266.
11. Capdevila, J. H.; Mosset, P.; Yadagiri, P.; Lumin, S.;
Falck, J. R. Arch. Biochem. Biophys. 1988, 261, 122–133.
12. (a) Fang, X.; Kaduce, T. L.; Weintraub, N. L.; Harmon,
S.; Teesch, L. M.; Morisseau, C.; Thompson, D. A.;
Hammock, B. D.; Spector, A. A. J. Biol. Chem. 2001,
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Scheme 2. Reagents and conditions: (a) CBr4, Ph3P, CH2Cl2,
0°C, 1 h (76%); (b) TMS–C2H, n-BuLi, THF, 0°C, 2 h; add
epoxy-bromide, −40°C to rt, 16 h (64%); (c) KF, MeOH,
60°C, 2 h (78%); (d) NIS, AgNO3, Me2CO, rt, 1 h (86%); (e)
KO2CNꢀNCO2K/AcOH, THF, rt, 16 h (88%); (f) 13b, Ag2O
(2.4 equiv.), Pd(dppf)Cl2 (10 mol%), K2CO3 (2.4 equiv.),
THF, 80°C, 8 h; (g) LiOH, THF/H2O (4:1), rt, 12 h.
13. Zou, G.; Reddy, Y. K.; Falck, J. R. Tetrahedron Lett.
2001, 42, 7213–7215.
14. Nicolaou, K. C.; Webber, S. E. Synthesis 1986, 453–461.
15. Spectral/physical data for 3: 1H NMR (400 MHz,
CDCl3): l 6.40 (dt, J=1.5, 7.0 Hz, 1H), 6.31 (apparent q,
J=7.0 Hz, 1H), 3.01–3.07 (m, 1H), 2.91–2.98 (m, 1H),
2.39 (td, J=7.9, 1.5 Hz, 2H), 1.28–1.64 (m, 8H), 0.91 (t,
J=7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): l 136.5,
84.9, 57.1, 54.8, 33.9, 31.7, 27.8, 26.3, 22.6, 14.1. Com-
Scheme 3. Reagents and conditions: (a) MeI, K2CO3, Me2CO,
60°C, 6 h (72%); (b) pinacolborane, Rh(Ph3P)3Cl, CH2Cl2, rt,
12 h; (c) NH4OAc, NaIO4, Me2CO/H2O (2:1), rt, 48 h.
instance, utilized boronic acid 13b. The antipodes of 5
and 10 were prepared by a brief, stereoselective inver-
sion sequence recently described by Falck et al.17
1
pound 6: H NMR (400 MHz, CDCl3): l 5.44–5.56 (m,
2H), 2.90–2.98 (m, 2H), 2.30–2.40 (m, 3H), 2.15–2.25 (m,
1H), 2.08–2.15 (m, 2H), 1.72 (quintet, J=7.6 Hz, 2H),
1.30–1.60 (m, 10H), 0.91 (t, J=6.7 Hz, 3H); 13C NMR
(75 MHz, CDCl3): l 174.2, 131.4, 125.4, 57.4, 56.7, 51.7,
33.6, 31.9, 27.9, 26.9, 26.4, 24.9, 22.8, 14.2. Compound 8:
1H NMR (400 MHz, CDCl3): l 6.40 (dt, J=1.5, 7.0 Hz,
1H), 6.32 (apparent q, J=7.0 Hz, 1H), 5.51–5.60 (m,
1H), 5.36–5.47 (m, 1H), 3.01–3.09 (m, 1H), 2.92–3.01 (m,
1H), 2.36–2.50 (m, 1H), 2.20–2.39 (m, 1H), 2.06 (appar-
ent q, J=7.02 Hz, 2H), 1.23–1.60 (m, 6H), 0.89 (t, J=6.7
Hz, 3H); 13C NMR (75 MHz, CDCl3): l 136.6, 133.3,
123.6, 85.2, 56.6, 55.0, 34.1, 31.7, 29.4, 27.6, 26.5, 22.7,
14.3. Compound 9: 1H NMR (400 MHz, CDCl3): l
5.37–5.59 (m, 4H), 3.67 (s, 3H), 2.89–2.98 (m, 2H),
2.35–2.47 (m, 2H), 2.32 (t, J=7.6 Hz, 2H), 2.15–2.27 (m,
2H), 2.01–2.12 (m, 4H), 1.23–1.70 (m, 10H), 0.89 (t,
J=6.7 Hz, 3H); 13C NMR (75 MHz, CDCl3): l 174.3,
133.1, 132.3, 124.6, 123.9, 56.7, 56.6, 51.7, 34.2, 31.7,
29.4, 29.2, 27.6, 27.3, 26.3, 24.7, 22.7, 14.3. Compound
The key boronic acids 13a,b were prepared from the
corresponding commercial unsaturated carboxylic acids
11 by hydroboration of the methyl esters 12 with
pinacolborane, and mild oxidative hydrolysis (Scheme
3).
Acknowledgements
Financial support provided by the Robert A. Welch
Foundation, NIH (GM 31278, DK 38226) and an
unrestricted grant from Taisho Pharmaceutical Co.,
Ltd.
References
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