2886
M. Miyazawa et al. / Tetrahedron Letters 45 (2004) 2883–2886
stirred at room temperature for 16 h. The reaction mixture
Acknowledgements
was diluted with diethyl ether, and the solution was filtered
through a Florisil pad. The pad was washed with diethyl
ether. The combined organic layer was concentrated under
reduced pressure. The residue was purified by column
chromatography on silica gel (eluent with hexane=ethyl
acetate ¼ 97 : 3) to afford 35 mg (70%) of 17a as a colorless
oil.
This research was financially supported by a Grant-in-
Aid from the Ministry of Education, Science, Sports and
Culture, Japan.
References and notes
(2S*,4S*,6S*)-2-ethoxy-4-phenyl-6-vinyltetrahydropyran:
1H NMR (400 MHz, CDCl3) d: 7.32–7.28 (m, 2H), 7.25–
7.23 (m, 1H), 7.22–7.18 (m, 2H), 5.89 (ddd, J ¼ 5:9, 10.8,
17.1 Hz, 1H), 5.28 (dd, J ¼ 0:9, 17.3 Hz, 1H), 5.13 (dd,
J ¼ 0:7, 10.5 Hz, 1H), 5.04 (d, J ¼ 2:9 Hz, 1H), 4.39 (dd,
J ¼ 5:3, 11.2 Hz, 1H), 3.80 (dq, J ¼ 9:5, 7.1 Hz, 1H), 3.53
(dq, J ¼ 9:5, 7.1 Hz, 1H), 3.24 (tt, J ¼ 3:8, 12.5 Hz, 1H),
1.95–1.97 (m, 2H), 1.81 (ddd, J ¼ 3:4, 12.9, 12.9 Hz, 1H),
1.57 (dt, J ¼ 12:4, 12.4 Hz, 1H,), 1.26 (t, J ¼ 7:1 Hz, 3H).
(2R*,4S*,6S*)-2-ethoxy-4-phenyl-6-vinyltetrahydropyran:
1H NMR (400 MHz, CDCl3) d: 7.32–7.28 (m, 2H), 7.25–
7.23 (m, 1H), 7.22–7.18 (m, 2H), 5.93 (ddd, J ¼ 5:3, 10.6,
17.3 Hz, 1H), 5.31 (ddd, J ¼ 1:5, 1.5, 17.3 Hz, 1H), 5.13
(ddd, J ¼ 1:5, 1.5, 10.7 Hz, 1H), 4.63 (dd, J ¼ 2:0, 9.4 Hz,
1H), 4.07–4.05 (m, 1H), 4.03 (dq, J ¼ 9:5, 7.1 Hz, 1H), 3.60
(dq, J ¼ 9:5, 7.1 Hz, 1H), 2.89 (tt, J ¼ 3:8, 12.5 Hz, 1H),
2.04 (dddd, J ¼ 1:9, 1.9, 3.9, 12.9 Hz, 1H), 1.85 (dddd,
J ¼ 1:9, 1.9, 3.9, 12.9 Hz, 1H), 1.67 (dt, J ¼ 9:6, 12.8 Hz,
1H), 1.54 (dt, J ¼ 12:5, 12.9 Hz, 1H), 1.26 (t, J ¼ 7:1 Hz,
3H).
(2S*,4S*,6R*)-2-ethoxy-4-phenyl-6-vinyltetrahydropyran:
1H NMR (400 MHz, CDCl3) d: 7.32–7.28 (m, 2H), 7.25–
7.23 (m, 1H), 7.22–7.18 (m, 2H), 6.29 (ddd, J ¼ 7:1, 10.4,
17.4 Hz, 1H), 5.23 (dd, J ¼ 1:7, 17.3 Hz, 1H), 5.12 (dd,
J ¼ 1:7, 10.2 Hz, 1H), 4.88 (dd, J ¼ 3:7, 7.3 Hz, 1H), 4.35–
4.28 (m, 1H), 3.88 (dq, J ¼ 9:8, 7.1 Hz, 1H), 3.47 (dq,
J ¼ 9:2, 7.1 Hz, 1H), 3.37 (tt, J ¼ 4:6, 9.2 Hz, 1H), 2.11–
1.88 (m, 4H), 1.22 (t, J ¼ 7:1 Hz, 3H).
1. (a) Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.;
Hwang, C.-K. J. Am. Chem. Soc. 1989, 111, 5335; (b)
Betancort, J. M.; Martin, V. S.; Padron, J. M.; Palazon, J.
M.; Ramirez, M. A.; Soler, M. A. J. Org. Chem. 1997, 62,
4570; (c) Ramirez, M. A.; Padron, J. M.; Palazon, J. M.;
Martin, V. S. J. Org. Chem. 1997, 62, 4584; (d) Vares, L.;
Rein, T. J. Org. Chem. 2002, 67, 7226; (e) Carruthers, W.
Cycloaddition Reactions in Organic Synthesis; Pergamon:
Oxford, 1990; (f) Kobayashi, S.; Jorgensen, K. A. Cyclo-
addition Reactions in Organic Synthesis; Wiley: Weinheim,
2002.
2. Hirai, Y.; Nagatsu, M. Chem. Lett. 1994, 21.
3. Yokoyama, H.; Otaya, K.; Kobayashi, H.; Miyazawa, M.;
Yamaguchi, S.; Hirai, Y. Org. Lett. 2000, 2, 2427.
4. Tsuji, J. Palladium Reagents and Catalysts: Innovations in
Organic Synthesis; Wiley: Chichester, 1995.
5. Unpublished results.
6. Miyazawa, M.; Hirose, Y.; Nakano, T.; Yokoyama, H.;
Yamaguchi, S.; Hirai, Y. Abstracts of Papers, 18th Inter-
national Congress of Heterocyclic Chemistry, Yokohama,
2001; Abstract 2-PO-78.
7. Walkup, R. D.; Boatman, P. D., Jr. Tetrahedron 1993, 49,
9285.
8. Recently, Pd(II) catalyzed cyclization of alkynyl aldehydes
and alkynyl ketones via hemiacetal intermediate were
reported. (a) Asao, N.; Nogami, T.; Takahashi, K.;
Yamamoto, Y. J. Am. Chem. Soc. 2002, 124, 764; (b)
Kato, K.; Yamamoto, Y.; Akita, H. Tetrahedron Lett.
2002, 43, 4915; (c) Nakamura, H.; Ohtaka, M.; Yamamoto,
Y. Tetrahedron Lett. 2002, 43, 7631; (d) Kato, K.; Tanaka,
M.; Yamamura, S.; Yamamoto, Y.; Akita, H. Tetrahedron
Lett. 2003, 44, 3089; (e) Miyakoshi, N.; Mukai, C. Org.
Lett. 2003, 5, 2335; (f) Mondal, S.; Nogami, T.; Asao, N.;
Yamamoto, Y. J. Org. Chem. 2003, 68, 9496.
(2R*,4S*,6R*)-2-ethoxy-4-phenyl-6-vinyltetrahydropyran:
1H NMR (400 MHz, CDCl3) d: 7.32–7.28 (m, 2H), 7.25–
7.23 (m, 1H), 7.22–7.18 (m, 2H), 6.03 (ddd, J ¼ 4:2, 10.9,
17.7 Hz, 1H), 5.32 (dd, J ¼ 1:7, 17.8 Hz, 1H), 5.24 (dd,
J ¼ 1:7, 10.9 Hz, 1H), 4.90 (dd, J ¼ 3:2, 8.9 Hz, 1H), 4.70
(m, 1H), 3.95 (dq, J ¼ 9:6, 7.1 Hz, 1H), 3.56 (dq, J ¼ 9:6,
7.1 Hz, 1H), 2.97 (tt, J ¼ 3:7, 12.6 Hz, 1H), 2.04 (dt,
J ¼ 3:1, 12.7 Hz, 1H), 1.94–1.91 (m, 2H), 1.74 (ddd,
J ¼ 8:7, 12.4, 12.4 Hz, 1H), 1.28 (t, J ¼ 7:1 Hz, 3H).
13C NMR (400 MHz, CDCl3) d: 145.43, 138.88, 128.47,
126.79, 126.30, 114.90, 97.17, 69.46, 62.49, 38.80, 38.05,
35.45, 15.19; IR (neat) 3063, 3028, 2930, 1647, 1454, 1375,
1335, 1125, 1060, 700, 519 cmꢀ1 ; MS (EI) : m=z 232(28,
Mþ), 187 (15), 186 (38); Anal. Calcd for C15H20O2: C,
77.55; H, 8.68. Found : C, 77.51; H, 8.93.
9. Dess, D. B.; Martin, J. C. J. Org. Chem. 1983, 48, 4155.
10. Representative procedure for the synthesis of 2-alkoxy-
4-phenyl-6-vinyltetrahydropyran: To
a
solution of
PdCl2(PhCN)2 (4 mg, 0.01 mmol) in THF (4.4 mL) was
added abs ethanol (0.03 mL, 0.47 mmol) and a solution of
aldehyde 15 (62 mg, 0.21 mmol) in THF (2 mL) at room
temperature under an argon atmosphere. The mixture was