F.-D. Boyer, I. Hanna / Journal of Organometallic Chemistry 691 (2006) 5181–5188
5187
4.3.3. Lactone 29b
Prepared from 16 by the same procedure as for 29a (63%)
using allyl alcohol instead of MeOH. H NMR: d = 5.93
article can be found, in the online version, at
1
(m, 1H), 5.33 (d, J = 17 Hz, 1H), 5.15 (d, J = 10 Hz, 1H),
4.92 (m, 1H), 4.19 (br s, 1H), 4.17 (br s, 1H), 4.13 (m,
1H), 2.40–1.30 (m, 12H), 1.10 (s, 3H). 13C NMR:
d = 175.3 (C), 172.7, (C), 135.3 (CH), 124.8 (C), 116.8
(CH2), 81.5 (CH), 70.9 (CH2), 65.8 (CH), 57.6 (CH3), 38.7
(CH2), 36.2 (C), 32.2 (CH2), 32.1 (CH2), 25.7(CH2), 25.6
(CH3), 23.0 (CH2), 22.0 (CH2). IR (CCl4): 1764 cmꢀ1. CI
MS: NH3 m/z 263 (M+Å+1), 280 (M+Å+18).
References
[1] For selected recent reports concerning the construction of (5–7) and
(6–7) bicyclic systems using transition metal-catalyzed reactions see:
M.A. Battiste, P.M. Pelphrey, D. Wright, Chem. Eur. J. 12 (2006),
and references cited therein;
B.M. Trost, H.C. Schen, D.B. Horne, F.D. Toste, B.G. Steinmetz,
C. Koradin, Chem. Eur. J. 11 (2005) 2577–2590;
M.W.B. Pfeiffer, A.J. Phillips, J. Am. Chem. Soc. 127 (2005) 5334–
5335;
P.A. Wender, F.C. Bi, M.A. Brodney, F. Gosselin, Org. Lett. 3
(2001) 2105–2108, and references cited therein;
R. Sarpong, J.T. Su, B.M.J. Stoltz, Am. Chem. Soc. 125 (2003)
13624–13625.
4.3.4. Ester 27 (major isomer)
Prepared by the two steps procedure from 12 as for 29a.
M.p. 78–80 °C (PE). H NMR: d = 6.23 (d, J = 11.6 Hz,
1
1H), 4.45 (d, J = 6 Hz, 1H), 4.12 (td, J = 11.6, 2.8 Hz,
1H), 3.82 (s, 3H), 3.36 (s, 3H), 2.30–1.42 (m, 10H), 1.31
(s, 3H). 13C NMR: d = 178.8 (C), d = 168.1, (C), 127.4
(C), 83.9 (CH), 69.7 (CH), 57.2 (CH3), 52.3 (CH3), 50.6
(C), 41.7 (CH2), 39.0 (CH2), 38.3 (CH2), 28.9 (CH3), 27.6
(CH2), 22.7 (CH2). IR (CCl4): 3409, 1691 cmꢀ1. CI MS:
NH3 m/z 255 (M+Å+1), 272 (M+Å+18). HMRS (EI) m/z
calc. for C14H22O4, 254.15181, found: 254.15280%.
[2] (a) For recent reviews concerning ring-closing metathesis reactions,
see: D. Astruc, New J. Chem. 29 (2005) 42–56;
(b) R.H. Grubbs, Tetrahedron 60 (2004) 7117–7140;
(c) R.H. Grubbs (Ed.), Handbook of Metathesis, Vol. 2, Wiley-VCH,
Weinheim, 2003;
(d) T.M. Trnka, R.H. Grubbs, Acc. Chem. Res. 34 (2001) 18–29;
(e) A. Furstner, Angew. Chem., Int. Ed. Engl. 39 (2000) 3012–
¨
3043;
(f) For a review on metathesis reactions in total syntheses see:
K.C. Nicolaou, P.G. Bulger, D. Sarlah, Angew Chem., Int.
Ed. Engl. 44 (2005) 4490–4527.
4.3.5. Epoxide 30
Prepared from 18 by the same procedure as for 28 and
used in the next step without further purification. Colorless
[3] (a) W.J. Zuercher, M. Scholl, R.H.J. Grubbs, Org. Chem. 63 (1998)
4291–4298;
(b) S.-H. Kim, W.J. Zuercher, N.B. Bowden, R.H.J. Grubbs, Org.
Chem. 61 (1996) 1073–1081;
(c) For a review see: S. Randl, S. Blechert, in: R.H. Grubbs (Ed.),
Handbook of Metathesis, Vol. 2, Wiley-VCH, Weinheim, 2003, pp.
151–175.
1
oil. H NMR: d = 7.37 (dd, J = 9, 5.1 Hz, 1H), 3.26 (t,
J = 4.2 Hz, 1H), 2.71–2.60 (m, 1H), 2.32–2.22 (m, 2H),
2.11–0.88 (m, 9H), 1.05 (s, 3H). 13C NMR: d = 166.9 (C),
149.6 (CH), 135.0 (C), 62.3 (C), 61.3 (CH), 51.6 (CH3),
42.6 (CH2), 36.8 (CH2), 32.8 (C), 27.4 (CH2), 24.0 (CH2),
21.8 (CH3), 21.6 (CH2), 16.7 (CH2). HMRS (EI) m/z calc.
for C14H20O3, 236.1413, found: 236.1413%.
[4] (a) P. Schwab, M.B. France, J.W. Ziller, R.H. Grubbs, Angew.
Chem., Int. Ed. Engl. 34 (1995) 2039–2041;
(b) M. Scholl, S. Ding, C.W. Lee, R.H. Grubbs, Org. Lett. 1 (1999)
953–956.
[5] (a) For recent reviews on enyne metathesis, see: M. Mori, in: R.H.
Grubbs (Ed.), Handbook of Metathesis, vol. 2, Wiley-VCH, Wein-
heim, 2003, pp. 176–204;
4.3.6. Lactone 31
(b) C.S. Poulsen, R. Madsen, Synthesis (2003) 1–18;
(c) S.T. Diver, A.J. Giessert, Chem. Rev. 104 (2004) 1317–1382;
(d) For a recent article on the selectivity of RCM enyne metathesis
see: E.C. Hansen, D.J. Lee, Am. Chem. Soc. 126 (2004) 15074–
15080.
Prepared from 27 by the same procedure as for 29a
(15 mg, 44%, 2 steps). White solid. 1H NMR: d = 7.22
(dd, J = 9, 5.1 Hz, 1H), 4.30 (t, J = 7.2 Hz, 1H), 2.84
(tdd, J = 10, 5.1, 3 Hz, 1H), 2.40–2.20 (m, 3H), 2.15–1.22
(m, 12H), 1.10 (s, 3H). 13C NMR: d = 168.8 (C), 145.1
(CH), 135.7 (C), 84.1 (CH), 78.3 (C), 40.6 (CH2), 34.8
(C), 32.7 (CH2), 25.5 (CH2), 23.2 (CH2), 22.4 (CH3), 21.8
[6] (a) For recent examples of synthesis of carbobicyclic systems by
metathesis of dienynes, see: E.M. Codesido, L. Castedo, J.R. Granja,
Org. Lett. 3 (2001) 1483–1486;
(b) R. Garcia-Fandino, E.M. Codesido, E. Sobarzo-Sanchez, L.
Castedo, J.R. Granja, Org. Lett. 6 (2004) 193–196.
[7] (a) For recent examples of synthesis of heterobicyclic systems by
metathesis of dienynes, see: T.-L. Choi, R. Grubbs, Chem. Commun.
(2001) 2648–2649;
(CH2), 16.1 (CH2). IR (film): 3444, 1724, 1674 cmꢀ1
.
HMRS (EI) m/z calc. for C13H18O3, 222.1256, found:
222.1270%.
(b) J. Huang, H. Xiong, R.P. Hsung, C. Rameshkumar, J.A. Mulder,
T.P. Grebe, Org. Lett. 4 (2002) 2417–2420;
Acknowledgements
(c) K. Shimizu, M. Takimoto, M. Mori, Org. Lett. 5 (2003) 2323–
2326;
We gratefully thank Dr. Louis Ricard (Ecole Polytech-
nique) for the X-ray structure determination of compound
27.
(d) C.-J. Wu, R.J. Madhushaw, R.-S.J. Liu, Org. Chem. 68 (2003)
7889–7892;
(e) T. Honda, H. Namiki, K. Kaneda, H. Mizutani, Org. Lett. 6
(2004) 87–89;
(f) K.P. Kaliappan, R.S. Nandurdikar, Chem. Commun. (2004)
2506–2507;
Appendix A. Supplementary material
Experimental procedures and characterization data for
dienynes 6–11. Supplementary data associated with this
(g) H. Fukumoto, K. Takahashi, J. Ishihara, S. Hatakeyama, Angew.
Chem., Int. Ed. Engl. 45 (2006) 2732–2734.