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2. (a)For reviews, see: Eicher, T., Hauptmann, S., Eds.The Chemistry of
Heterocycles: Structure, Reactions, Syntheses, and Applications; Wiley-VCH:
Weinheim, 2003; (b)Common Fragrance and Flavor Materials; Bauer, K., Garbe,
D., Eds.; VCH: Weinheim, 1985; (c) Vernin, G. The Chemistry of Heterocyclic
Flavouring and Aroma Compounds; Ellis Horwood: Chichester, 1982.
3. For reviews, see: (a) Maier, M. In Organic Synthesis Highlights II; Waldmann, H.,
Ed.; VCH: Weinheim, 1995; p 231; (b)Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; (c) Lipshutz, B. H. Chem.
Rev. 1986, 86, 795.
4. (a) Zhang, L.-Z.; Chen, C.-W.; Lee, C.-F.; Wu, C.-C.; Luh, T.-Y. Chem. Commun.
2002, 2336; (b) Wu, C.-C.; Hung, W.-Y.; Liu, T.-L.; Zhang, L.-Z.; Luh, T.-Y. J. Appl.
Phys. 2003, 93, 5465; (c) Lin, S.-Y.; Chen, I.-W. P.; Chen, C.-H.; Lee, C.-F.; Chou,
C.-M.; Luh, T.-Y. J. Phys. Chem. B 2005, 109, 7915; (d) Tsuji, H.; Mitsui, C.; Ilies,
L.; Sato, Y.; Nakamura, E. J. Am. Chem. Soc. 2007, 129, 11902; (f) Chen, I.-W. P.;
Fu, M.-D.; Tseng, W.-H.; Chen, C.-H.; Chou, C.-M.; Luh, T.-Y. Chem. Commun.
2007, 3074.
12. (a) Venus-Danilova, E. D.; Al’bitskaya, V. M. Zh. Obshch. Khim. 1952, 22, 816; (b)
Utimoto, K. Pure Appl. Chem. 1983, 55, 1845; (c) Sham, H. L.; Betebenner, D. A. J.
Chem. Soc., Chem. Commun. 1991, 1134; (d) Tani, K.; Sato, Y.; Okamoto, S.; Sato,
F. Tetrahedron Lett. 1993, 34, 4975; (e) Pasha, M. K.; Ahmad, F. Lipids 1993, 28,
1027; (f) Trost, B. M.; McIntosh, M. C. J. Am. Chem. Soc. 1995, 117, 7255; (g)
Schmidt, B.; Kocienski, P.; Reid, G. Tetrahedron 1996, 52, 1617; (h) Stephen, A.;
Hashmi, K.; Schwarz, L. Chem. Ber. 1997, 130, 1449; (i) Marshall, J. A.; Sehon, C.
A. Org. Synth. 1999, 76, 263; (j) Qing, F.-L.; Gao, W.-Z.; Ying, J. J. Org. Chem. 2000,
65, 2003; (k) Zhang, D.; Yuan, C. Eur. J. Org. Chem. 2007, 3916; (l) Wen, S.-g.; Liu,
W.-m.; Liang, Y.-m. Synthesis 2007, 3295; (m) Hayes, S. J.; Knight, D. W.;
Menzies, M. D.; O’Halloran, M.; Tan, W.-F. Tetrahedron Lett. 2007, 48, 7709; (n)
Bew, S. P.; El-Taeb, G. M. M.; Jones, S.; Knight, D. W.; Tan, W.-F. Eur. J. Org. Chem.
2007, 5759; (o) Arimitsu, S.; Jacobsen, J. M.; Hammond, G. B. J. Org. Chem. 2008,
73, 2886; (p) Yada, Y.; Miyake, Y.; Nishibayashi, Y. Organometallics 2008, 27,
3614.
13. (a) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.; Milton, M. D.; Hidai, M.; Uemura,
S. Angew. Chem., Int. Ed. 2003, 42, 2681; (b) Yin, G.; Wang, Z.; Chen, A.; Gao, M.;
Wu, A.; Pan, Y. J. Org. Chem. 2008, 73, 3377.
14. (a) Tseng, H.-R.; Luh, T.-Y. J. Org. Chem. 1997, 62, 4568; (b) Tseng, H.-R.; Lee, C.-
F.; Yang, L.-M.; Luh, T.-Y. J. Org. Chem. 1999, 64, 8582.
5. For recent reviews, see: (a) Hou, X. L.; Cheung, H. Y.; Hon, T. Y.; Kwan, P. L.; Lo,
T. H.; Tong, S. Y.; Wong, H. N. C. Tetrahedron 1998, 54, 1955; (b) Keay, B. A.
Chem. Soc. Rev. 1999, 28, 209; (c) Hou, X.-L.; Yang, Z.; Wong, H. N. C. Prog.
Heterocycl. Chem. 2001, 13, 130.
6. (a) Marshall, J. A.; Robinson, E. D. J. Org. Chem. 1990, 55, 3450; (b) Marshall, J. A.;
Wang, X. J. Org. Chem. 1991, 56, 960; (c) Marshall, J. A.; Bartley, G. S. J. Org.
Chem. 1994, 59, 7169; (d) Marshall, J. A.; Wallace, E. M. J. Org. Chem. 1995, 60,
796.
7. (a) Ma, S.; Li, L. Org. Lett. 2000, 2, 941; (b) Hashmi, A. S. K.; Schwarz, L.; Choi, J.-
H.; Frost, T. M. Angew. Chem., Int. Ed. 2000, 39, 2285; (c) Kel’in, A. V.; Gevorgyan,
V. J. Org. Chem. 2002, 67, 95; (d) Ma, S.; Zhang, J.; Lu, L. Chem. Eur. J. 2003, 9,
2447–2456; (e) Sromek, A. W.; Rubina, M.; Gevorgyan, V. J. Am. Chem. Soc.
2005, 127, 10500; (f) Schwier, T.; Sromek, A. W.; Yap, D. M. L.; Chernyak, D.;
Gevorgyan, V. J. Am. Chem. Soc. 2007, 129, 9868; (g) Dudnik, A. S.; Sromek, A.
W.; Rubina, M.; Kim, J. T.; Kel’in, A. V.; Gevorgyan, V. J. Am. Chem. Soc. 2008, 130,
1440.
8. (a) Lee, C.-F.; Yang, L.-M.; Hwu, T.-Y.; Feng, A.-H.; Tseng, J.-C.; Luh, T.-Y. J. Am.
Chem. Soc. 2000, 122, 4992; (b) Lee, C.-F.; Liu, C.-Y.; Song, H.-C.; Luo, S.-J.; Tseng,
J.-C.; Tso, H.-H.; Luh, T.-Y. Chem. Commun. 2002, 2824–2825; (c) Liu, C-Y.; Luh,
T.-Y. Org. Lett. 2002, 4, 4305–4307; (d) Tseng, J.-C.; Lin, H.-C.; Huang, S.-L.; Lin,
C.-L.; Jin, B.-Y.; Chen, C.-Y.; Yu, J.-K.; Chou, P.-T.; Luh, T.-Y. Org. Lett. 2003, 5,
4381; (e) Tseng, J.-C.; Chen, J.-H.; Luh, T.-Y. Synlett 2006, 1209; (f) Chou, C.-M.;
Chen, W.-Q.; Chen, J.-H.; Lin, C.-L.; Tseng, J.-C.; Lee, C.-F.; Luh, T.-Y. Chem. Asian
J. 2006, 1, 46–55; (g) Lin, H.-C.; Lin, W.-Y.; Bai, H.-T.; Chen, J.-H.; Jin, B.-Y.; Luh,
T.-Y. Angew. Chem., Int. Ed. 2007, 46, 897–900; (h) Lin, C.-L.; Chou, C.-M.; Luh,
T.-Y. J. Org. Chem. 2007, 72, 8531–8534.
9. For reviews on the use of propargylic dithioacetals, see: (a) Luh, T.-Y. Pure Appl.
Chem. 2005, 77, 1213; (b) Luh, T.-Y.; Lee, C.-F. Eur. J. Org. C 2005, 3839; (c) Luh,
T.-Y.; Lin, H.-C.; Chou, C.-M. Pure Appl. Chem. 2008, 80, 475.
10. (a) Marshall, J. A.; DuBay, W. J. J. Org. Chem. 1993, 58, 3435; (b) Kim, S.; Kim, Y.
G. Synlett 1991, 869; (c) Fukuda, Y.; Shiragami, H.; Utimoto, K.; Nozaki, H. J. Org.
Chem. 1991, 56, 5816.
11. (a) Babudri, F.; Cicco, S. R.; Farinola, G. M.; Lopez, L. C.; Naso, F.; Pinto, V. Chem.
Commun. 2007, 3756; (b) Fu, Z.; Wang, M.; Ma, Y.; Liu, Q.; Liu, J. J. Org. Chem.
2008, 73, 7625.
15. (a) Huang, L.-F.; Chen, C.-W.; Luh, T.-Y. Org. Lett. 2007, 9, 3363; (b) Chen, C.-W.;
Luh, T.-Y. J. Org. Chem. 2008, 73, 8357.
16. Typical procedure for the preparation of homopropargylic alcohol 7: At ꢀ78 °C,
under N2 atmosphere, to a THF (50 mL) solution of 5a (1.14 g, 5 mmol) was
added nBuLi (2.4 mL, 2.5 M in hexane, 6 mmol) dropwise and the mixture was
stirred for 1 h. p-Anisaldehyde 6f (0.61 mL, 5 mmol) in THF (10 mL) was then
added dropwise and the mixture was gradually warmed to rt and stirred for
8 h, quenched with satd NH4Cl, washed with brine, and extracted with ether.
The organic layer was dried (MgSO4), filtered, and the filtrate was evaporated
in vacuo to give the residue which was chromatographed on silica gel (hexane/
ethyl acetate = 30/1) to give 7f (dr ratio = 6.4/1) in 84% yield: major isomer: 1H
NMR (CDCl3, 400 MHz): d 0.92 (t, J = 7.0 Hz, 3H), 0.94 (t, J = 7.0 Hz, 3H), 1.11 (d,
J = 6.5 Hz, 6H), 1.34–1.47 (m, 4H), 1.48–1.58 (m, 4H), 1.84 (sept, J = 6.5 Hz, 1H),
2.29 (t, J = 7.0 Hz, 2H), 2.47 (t, J = 7.4 Hz, 2H), 2.51–2.72 (m, 4H), 3.04 (d,
J = 6.0 Hz, 1H), 3.82 (s, 3H), 4.74 (d, J = 6.0 Hz, 1H), 6.82–6.88 (m, 2H), 7.42–
7.47 (m, 2H); characteristic 1H NMR signals for the minor isomer: d 3.90 (s, 3H),
4.78 (d, J = 4.8 Hz, 1H).
17. Typical procedure for the preparation of 9: A mixture of 7f (167 mg, 0.5 mmol)
and Hg(OAc)2 (319 mg, 1.0 mmol) in THF (5 mL) was stirred at rt for 18 h. KI
(249 mg, 1.5 mmol) and I2 (381 mg, 1.5 mmol) were then added and the
mixture was further stirred for 3 h, quenched with satd Na2S2O3, and extracted
with ether. The organic layer was washed with 10% Na2Sꢁ9H2O, dried (MgSO4),
filtered, and the filtrate was evaporated in vacuo to give the residue which was
chromatographed (hexane/chloroform = 30/1) on silica gel to give 9f as a
colorless liquid (153 mg, 77%): 1H NMR (CDCl3, 400 MHz): d 0.97 (t, J = 7.2 Hz,
3H), 1.34 (d, J = 7.2 Hz, 6H), 1.36–1.48 (m, 2H), 1.62–1.72 (m, 2H), 2.72 (t,
J = 7.6 Hz, 2H), 3.18 (sept, J = 7.2 Hz, 1H), 6.92–6.97 (m, 2H), 7.36–7.41 (m, 2H);
13C NMR (100 MHz, CDCl3): d 14.0, 21.6, 22.4, 26.2, 27.6, 30.3, 55.3, 65.8, 113.7,
124.1, 125.7, 129.0, 147.5, 155.3, 158.9; HRMS (FAB) calcd for C18H23O2I:
398.0743, found: 398.0748.