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T. G. Kilroy et al.
FEATURE ARTICLE
1H NMR (500 MHz): d = 0.83 (d, 6 H, J = 7 Hz), 0.91 (d, 6 H, J = 7
Hz,), 1.90 (hept, 2 H, J = 7 Hz), 1.81 (t, 2 H, J = 4 Hz), 2.0 (m, 2 H),
5.46 (dd, 1 H, J = 1, 6 Hz).
13C NMR (75 MHz): d = 17.9, 18.4, 19.4, 19.8, 26.4, 33.4, 34.6,
34.9, 93.0, 102.0.
MS (EI, 70 eV): m/z (%) = 154 (M+ – 18, 16), 129 (19), 111 (45),
93 (100), 83 (22).
(5) For recent reviews of the asymmetric Heck reaction see:
(a) Guiry, P. J.; Hennessy, A. J.; Cahill, J. P. Top. Catal.
1997, 4, 311. (b) Shibasaki, M.; Vogl, E. M. J. Organomet.
Chem. 1999, 576, 1. (c) Gibson, S. E.; Middleton, R. J.
Contemp. Org. Synth. 1996, 3, 447. (d) Donde, Y.;
Overman, L. E. Catalytic Asymmetric Synthesis; Oijima, I.,
Ed.; Wiley-VCH: New York, 2000, Chap. 8g.
(e) Shibasaki, M.; Miyazaki, F. Handbook of
Organopalladium Chemistry for Organic Synthesis;
Negishi, E., Ed.; Wiley-VCH: Weinheim, 2002, 1283–1315.
(6) (a) Dounay, A. B.; Overman, L. E. Chem. Rev. 2003, 103,
2945. (b) Guiry, P. J.; Kiely, D. Curr. Org. Chem. 2004, 8,
781.
(7) Ozawa, F.; Kubo, A.; Hayashi, T. Tetrahedron Lett. 1992,
33, 1485.
(8) Loiseleur, O.; Meier, O.; Pfaltz, A. Angew. Chem., Int. Ed.
Engl. 1996, 35, 200.
(9) (a) Gilbertson, S. R.; Fu, Z. Org. Lett. 2001, 3, 161.
(b) Gilbertson, S. R.; Xie, D.; Fu, Z. J. Org. Chem. 2001, 66,
7420. (c) Gilbertson, S. R.; Fu, Z.; Xie, D. Tetrahedron Lett.
2001, 42, 365. (d) Hashimoto, Y.; Horie, Y.; Hayashi, M.;
Saigo, K. Tetrahedron: Asymmetry 2000, 11, 2205. (e) Tu,
T.; Deng, W.-P.; Hou, X.-L.; Dai, l.-X.; Dong, X.-C. Chem.–
Eur. J. 2003, 9, 3073.
(10) Kilroy, T. G.; Hennessy, A. J.; Malone, Y. M.; Farrell, A.;
Guiry, P. J. J. Mol. Catal. A: Chem. 2003, 196, 65.
(11) (a) Kiely, D.; Guiry, P. J. Tetrahedron Lett. 2002, 43, 9545.
(b) Kiely, D.; Guiry, P. J. Tetrahedron Lett. 2003, 44, 7377.
(c) Kiely, D.; Guiry, P. J. J. Organomet. Chem. 2003, 687,
545.
(12) Kündig, P. E.; Meier, P. Helv. Chim. Acta 1999, 82, 1360.
(13) Malkov, A. V.; Bella, M.; Stara, I. G.; Kocovsky, P.
Tetrahedron Lett. 2001, 42, 3045.
(14) Tietze, L. F.; Lohmann, J. K. Synlett 2002, 2083.
(15) Cozzi, P. G.; Menges, F.; Kaiser, S. Synlett 2003, 833.
(16) Kilroy, T. G.; End, N.; Cozzi, P. G.; Guiry, P. J. Synlett
2004, 106.
2,2-Diisopropyl-2,3-dihydrofuran (28)
5,5-Diisopropyltetrahydrofuran-2-ol (160 mg, 0.93 mmol) was dis-
solved in anhyd CH2Cl2 (5 mL), cooled to –20 °C under nitrogen,
and treated with NEt3 (0.39 mL, 2.79 mmol) followed by trifluo-
romethanesulfonyl chloride (0.1 mL, 1.21 mmol). The resultant
white suspension was stirred at –20 °C for 30 min and then refluxed
for 2.5 h. The mixture was then diluted with CH2Cl2, washed with
H2O, dried (Na2SO4) and concentrated affording a red oil which was
purified by column chromatography (pentane–CH2Cl2, 4:1;
Rf = 0.5) to afford 28 (86 mg, 60%) as a colourless oil.
IR (film): 3081, 2965, 2933, 2877, 2305, 1623 (C=C), 1473, 1265,
1061, 748 cm–1.
1H NMR (500 MHz): d = 0.87 (dd, 12 H, J = 6.7 Hz), 1.90 (m, 2
H), 2.33 (app t, 2 H, 2.4 Hz), 4.71 (m, 1 H), 6.24 (m, 1 H).
13C NMR (75 MHz): d = 15.18, 15.39 (2 × CH3), 31.33 (CH), 32.83
(C3), 92.05 (C2), 97.81 (C4), 144.70 (C5).
MS (EI, 70 eV): m/z (%) = 154 (M+, 12), 129 (14), 111 (36), 93
(100), 83 (18).
Anal. Calcd for C10H18O: C, 77.87; H, 11.76. Found: C, 77.52; H,
11.56.
Acknowledgements
T. G. K. thanks Enterprise Ireland for the award of a Research Scho-
larship (BR/99/240) and a postdoctoral award (SC/2002/349). The
award from Merck Frosst of a Visiting Professorship to P. J. G. at
the University of Toronto, where this manuscript was prepared, is
gratefully acknowledged.
(17) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34,
2015.
(18) End, N.; Stoessel, C.; Berens, U.; di Pietro, P.; Cozzi, P. G.
submitted to Tetrahedron: Asymmetry; Special Issue on
phosphorous ligands.
(19) Ozawa, F.; Kubo, A.; Matsumoto, Y.; Hayashi, T.
Organometallics 1993, 12, 4188.
(20) (a) Hennessy, A. J.; Malone, Y. M.; Farrell, A.; Guiry, P. J.
Tetrahedron Lett. 1999, 40, 9163. (b) Hennessy, A. J.;
Malone, Y. M.; Farrell, A.; Guiry, P. J. Tetrahedron Lett.
2000, 41, 2261. (c) Hennessy, A. J.; Connolly, D. J.;
Malone, Y. M.; Farrell, A.; Guiry, P. J. Tetrahedron Lett.
2000, 41, 7757.
(21) For a review of alkannin and shikonin natural products, see:
Papageorgiou, V. P.; Assimopoulou, A. N.; Couladouros, E.
A.; Hepworth, D.; Nicolaou, K. C. Angew. Chem., Int. Ed.
1999, 38, 270.
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Synthesis 2004, No. 11, 1879–1888 © Thieme Stuttgart · New York