2234
T. Hirabayashi et al. / Tetrahedron 62 (2006) 2231–2234
flask. To this solution are added alkyne (1 mmol) and
alcohol (3 mmol) at room temperature. The reaction was
carried out at 70 8C for 15 h. Removal of the solvent under
reduced pressure afforded a cloudy solution, which was
purified by column chromatography on silica gel (n-hexane/
ethyl acetateZ15:1) to give the corresponding product. The
References and notes
1. For example, see Tokunaga, M.; Larrow, J. F.; Kakiuchi, F.;
Jacobsen, E. N. Science 1997, 277, 936.
2. Larock, R. C.; Leong, W. W. In Trost, B. M., Flemming, I.,
Semmelhock, M. F., Eds.; Comprehensive Organic Synthesis;
Pergamon: Oxford, 1991; Vol. 4, p 269. March, J. Advanced
Organic Chemistry; Wiley: New York, 1992; p 762.
3. Kataoka, Y.; Matsumoto, O.; Tani, K. Chem. Lett. 1996, 727.
4. Harman, W. D.; Dobson, J. C.; Taube, H. J. Am. Chem. Soc.
1989, 111, 3061.
1
products were characterized by H and 13C NMR, IR, and
GC–MS, respectively.
1
3.3.1. 2-Hexyl-2-methyl-1,3-dioxolane (4ae). H NMR d
3.97–3.90 (m, 4H), 1.65–1.61 (t, JZ6.7 Hz, 2H), 1.38–1.29
(m, 11H), 0.90–0.87 (t, JZ7.2 Hz, 3H); 13C NMR d 110.2,
64.5, 39.2, 31.7, 29.4, 24.0, 23.8, 22.5, 14.0; IR (NaCl)
2932, 2873, 1208, 1080 cmK1; HRMS (EI): calcd for
C10H20O2 [MKH]C: 172.1463; found: 172.1466.
5. Kamijo, S.; Yamamoto, Y. J. Org. Chem. 2003, 68, 4764.
6. (a) Hiscox, W.; Jennings, P. W. Organometallics 1990, 9,
1997. (b) Hartman, J. W.; Hiscox, W. C.; Jennings, P. W.
J. Org. Chem. 1993, 58, 7613. (c) Kataoka, Y.; Matsumoto, O.;
Ohashi, M.; Yamagata, T.; Tani, K. Chem. Lett. 1994, 1283.
(d) Kataoka, Y.; Matsumoto, O.; Tani, K. Organometallics
1996, 15, 5246.
3.3.2. 4-Ethyl-2-hexyl-2-methyl-1,3-dioxolane (4af). 1H
NMR d 3.96–3.87 (m, 3H), 1.63–1.58 (t, JZ6.7 Hz, 2H),
1.44–1.28 (m, 13 H), 0.92–0.86 (m, 6H); 13C NMR d 110.9,
68.8, 62.8, 40.6, 32.1, 29.9, 25.2, 24.6, 23.2, 22.8, 14.8; IR
(NaCl) 2944, 2877, 1221, 1099 cmK1; HRMS (EI): calcd
for C12H24O2 [MKH]C: 200.1776; found: 200.1772.
7. Blum, J.; Huminer, H.; Alper, H. J. Mol. Catal. 1992, 75, 153.
8. Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104,
3079 and these reference.
9. (a) Tokunaga, M.; Wakatsuki, Y. Angew. Chem., Int. Ed. 1998,
37, 2867. (b) Tokunaga, M.; Suzuki, T.; Koga, N.; Fukushima,
T.; Horiuchi, A.; Wakatsuki, Y. J. Am. Chem. Soc. 2001, 123,
11917.
3.3.3. 2-Hexyl-2-methyl-4-pentyl-1,3-dioxolane (4ag). 1H
NMR d 3.99–3.89 (m, 3H), 1.68–1.64 (t, JZ6.7 Hz, 2H),
1.49–1.26 (m, 19 H), 0.92–0.86 (m, 6H); 13C NMR d 112.6,
69.2, 62.2, 39.6, 33.2, 31.1, 29.4, 24.8, 24.2, 23.2, 22.9,
18.2, 14.1; IR (NaCl) 2932, 2873, 1208, 1080 cmK1; HRMS
(EI): calcd for C15H30O2 [MKH]C: 242.2246; found:
242.2250.
10. Mizushima, E.; Sato, K.; Hayashi, T.; Tanaka, M. Angew.
Chem., Int. Ed. 2002, 41, 4563.
11. Ogo, S.; Uehara, K.; Abura, T.; Watanabe, Y.; Fukuzumi, S.
J. Am. Chem. Soc. 2004, 126, 16520.
12. Nakagawa, H.; Okimoto, Y.; Sakaguchi, S.; Ishii, Y.
Tetrahedron Lett. 2003, 44, 103.
13. In the reaction with 2e, a small amount of 2-chloro-1-octene
was formed as a side-product. Although a detail of the reaction
pathway is unclear at this stage, it may be possible that the
present Ir-catalyzed addition of alcohol or water to terminal
alkyne is initiated by adding of HCl, which is generated from
ZrCl4, followed by alcoholysis or hydrolysis to give the
corresponding adduct.
Acknowledgements
This work was partially supported by a Grant-in-Aid for
Scientific Research on Priority Areas from the Ministry of
Education, Science and Culture, Culture, Japan, and Daicel
Chemical Industries Ltd.
14. Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 2049.