Asymmetric Synthesis of Massoialactones
1501
(6R)-6-Pentyl-5,6-dihydro-2H-2-pyranone ((R)-1)
To a stirred solution of ester (R)-8 (0.92 g, 2.93 mmol) in MeOH (15 mL), a
pinch of PTSA was added. The reaction mixture was allowed to stir for
30 min at room temperature. Methanol was removed in vacuum, and then
benzene (15 ml) was added to the reaction mixture and stirred for 1 h at
room temperature. Followed by TLC, the reaction mixture was concentrated
under reduced pressure. The crude product was purified by column chromato-
graphy using silica gel to give a lactone (R)-1 (0.372 g, 76%). [a]D 2113.5 (c
1, CHCl3), lit.[6e] [a]D 2110.7 (c 1, CHCl3); IR (neat): 2933, 1725, 1617,
1
1039 cm21; H NMR (300 MHz, CDCl3): d 6.80–6.87 (m, 1H), 5.96–6.02
(m, 1H), 4.33–4.44 (m, 1H), 2.27–2.35 (m, 2H), 1.25–1.86 (m, 8H), 0.91
(t, J ¼ 6.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): 164.57, 144.99, 121.43,
78.0, 34.79, 31.54, 29.35, 24.47, 22,46, 13.94; LCMS: 191 (M þ Na).
(6S)-6-Pentyl-5,6-dihydro-2H-2-pyranone ((S)-1)
Compound (S)-1 was similarly obtained in 74% yield from (S)-8: liquid, [a]D
þ104.8 (c 0.41, CHCl3), lit.[9] [a]D þ109.6 (c 2.0, CHCl3).
ACKNOWLEDGMENT
P. G. thanks Council of Scientific and Industrial Research (CSIR), New Delhi,
for the award of a fellowship.
REFERENCES
1. (a) Reddy, M. V. R.; Yucel, A. J.; Ramachandran, P. V. J. Org. Chem. 2001, 66,
2512; (b) Reddy, M. V. R.; Rearick, J. P.; Hoch, N.; Ramachandran, P. V. Org.
Lett. 2001, 3, 19; (c) Smith, A. B.; Brandt, B. M. Org. Lett. 2001, 3, 1685;
(d) Boger, D. L.; Ichikawa, L.; Zhong, W. J. Am. Chem. Soc. 2001, 123, 4161;
(e) Gosh, A. K.; Bilcer, G. Tetrahedron Lett. 2000, 41, 1003.
2. Abe, S. J. Chem. Soc. Jpn. 1937, 58, 246.
3. Hashizune, T.; Kikuchi, N.; Sagaki, Y.; Sakata, I. Agric. Biol. Chem. 1968, 32,
1306.
4. Kaiser, R.; Lamparsky, D. Tetrahedron Lett. 1976, 1659.
5. Cavill, G. W. K.; Clark, D. V.; Whitfield, F. B. Aust. J. Chem. 1968, 21, 2819.
6. (a) Crombie, L. J. Chem. Soc. 1955, 1007; (b) Nobuhara, A. J. Agric. Biol. Chem.
1968, 32, 1016; (c) Abe, S.; Sato, K. Bull. Chem. Soc. Jpn. 1956, 29, 88;
(d) Mori, K. Agric. Biol. Chem. 1976, 40, 1617; (e) Fournier, L.; Kocienski, P.;
Pons, J. M. Tetrahedron 2004, 60, 1659; (f) Sato, M.; Nakashima, H.;
Hanada, K.; Hayashi, M.; Honzumi, M.; Taniguchi, T.; Ogasawara, K. Tetrahe-
dron Lett. 2001, 42, 2833; (g) Kiyooka, S.-I.; Hena, M. A. J. Org. Chem. 1999,
64, 5511.