M.-J. Wu, C.-L. Lee, Y.-C. Wu, C.-P. Chen
(4R)-Rollicosin (2): A mixture of 19 (78 mg, 0.2 mmol) and pale yellow oil. 1H NMR (CDCl3, 400 MHz): δ = 7.25 (d, J =
FULL PAPER
[Rh(PPh3)3Cl] (0.2 g, 0.2 mmol) in benzene/methanol (1:1, 2 mL)
was stirred under hydrogen (1 atm) at room temperature for 24 h.
After removal of the solvent, the residue was purified by column
chromatography [silica gel, n-hexane/EtOAc (2:1) as eluent] to give
1.2 Hz, 1 H), 5.09–5.04 (m, 1 H), 4.41 (td, J = 7.6, 4.4 Hz, 1 H),
4.06–3.97 (m, 1 H), 3.59–3.47 (m, 1 H), 2.65–2.48 (m, 6 H), 2.28–
2.17 (m, 3 H), 2.16–2.06 (m, 1 H), 1.60–1.28 (m, 11 H) ppm. 13C
NMR (CDCl3, 50 MHz): δ = 177.4, 174.6, 152.7, 130.2, 83.0, 78.3
(2 C), 78.2, 77.3, 73.9, 73.3, 72.8, 68.1, 32.6, 32.2, 28.7, 28.5, 27.9,
2 (63 mg, 80 %) as a white solid, m.p. 107–108 °C [ref.[5d] 104–
1
106 °C]. H NMR (CDCl3, 400 MHz): δ = 7.18 (d, J = 1.6 Hz, 1 24.8, 24.0, 19.0, 18.9 ppm. MS (EI): m/z (%) = 388 (26) [M]+, 218
H), 5.12–5.02 (m, 1 H), 4.42 (td, J = 7.6, 4.4 Hz, 1 H), 3.87–3.78
(30), 141 (99). HRMS (EI): calcd. for C22H28O6 388.1886; found
(m, 1 H), 3.59–3.50 (m, 1 H), 2.66–2.42 (m, 3 H), 2.40–2.36 (m, 1 388.1882. [α]2D5 = +17.2 (c = 1.0, CHCl3).
H), 2.29–2.20 (m, 1 H), 2.16–2.04 (m, 2 H), 1.60–1.46 (m, 8 H),
(4S)-Rollicosin (3): Prepared following the procedure used for rol-
1.43 (d, J = 6.8 Hz, 3 H), 1.39–1.20 (m, 13 H) ppm. 13C NMR
(CDCl3, 50 MHz): δ = 177.1, 174.6, 151.8, 131.2, 82.9, 78.0, 73.6,
70.0, 37.4, 33.3, 33.0, 29.4 (2 C), 28.7, 25.5, 25.4, 24.1, 19.1 ppm.
MS (EI): m/z (%) = 396 (5) [M]+, 267 (25), 73 (99). HRMS (EI):
calcd. for C22H36O6 396.2512; found 396.2517. [α]2D5 = +1.9 (c =
1
licosin (2) in 80% yield as a white solid, m.p. 86–87 °C. H NMR
(CDCl3, 400 MHz): δ = 7.18 (d, J = 1.2 Hz, 1 H), 5.10–5.02 (m, 1
H), 4.41 (td, J = 7.2, 4.4 Hz, 1 H), 3.87–3.79 (m, 1 H), 3.58–3.50
(m, 1 H), 2.67–2.42 (m, 3 H), 2.40–2.36 (m, 1 H), 2.29–2.21 (m, 1
H), 2.16–2.04 (m, 2 H), 1.60–1.46 (m, 8 H), 1.42 (d, J = 6.8 Hz, 3
H), 1.39–1.20 (m, 13 H) ppm. 13C NMR (CDCl3, 50 MHz): δ =
177.1, 174.6, 152.0, 131.1, 82.9, 78.0, 73.6, 69.8, 37.4, 33.4, 33.0,
29.4, 29.3, 28.7, 25.5, 25.3, 24.1, 19.1 ppm. MS (EI): m/z (%) =
396 (7) [M]+, 267 (99), 112 (90). HRMS (EI): calcd. for C22H36O6
396.2512; found 396.2518. [α]2D5 = +7.5 (c = 1.0, CHCl3).
1.0, CHCl3) {ref.[4] [α]2D4 = –26.0 (c = 0.05, CHCl3); ref.[5d] [α]2D4
+2.5 (c = 0.29, CHCl3)].
=
(5S)-5-Methyl-3-[(2R)-oxiran-2-ylmethyl]-3-(phenylthio)-4,5-dihy-
drofuran-2(3H)-one (20): Prepared following the procedure used for
compound 15 by Method B using (R)-epichlorohydrin as the start-
1
ing material in 55% yield as a pale yellow oil. H NMR (CDCl3,
Owing to the small quantities of the final products 2 and 3, we
were unable to obtain elemental analysis data. In order to prove
the purity of the two final products 2 and 3 – within the limits of
200 MHz): δ = 7.60–7.50 (m, 2 H), 7.46–7.30 (m, 3 H), 4.72–4.56
(m, 1 H), 2.99–2.92 (m, 1 H), 2.87–2.73 (m, 2 H), 2.50–2.46 (m, 1
H), 2.24 (dd, J = 11.0, 3.6 Hz, 1 H), 2.01 (dd, J = 7.6, 6.4 Hz, 1
H), 1.75 (dd, J = 8.0, 6.4 Hz, 1 H), 1.27 (d, J = 6.4 Hz, 3 H) ppm.
13C NMR (CDCl3, 50 MHz): δ = 176.4, 137.0 (2 C), 130.0, 129.8,
129.0 (2 C), 73.6, 54.3, 48.8, 46.0, 39.9, 39.7, 21.6 ppm. MS (EI):
m/z (%) = 264 (90) [M]+, 135 (35), 110 (95). HRMS (EI): calcd. for
C14H16O3Si 264.0820; found 264.0811.
1
this method – the H and 13C NMR spectra of these products are
given (see electronic supporting information).
Supporting Information (see also the footnote on the first page of
1
this article): The H and 13C NMR spectra of the two final prod-
ucts 2 and 3.
(5S)-5-Methyl-3-[(2R)-oxiran-2-ylmethyl]furan-2(5H)-one (21): Pre-
pared following the procedure used for compound 16 in 90% yield
1
as a pale yellow oil. H NMR (CDCl3, 200 MHz): δ = 7.21 (d, J =
Acknowledgments
1.6 Hz, 1 H), 4.98 (qd, J = 6.8, 1.6 Hz, 1 H), 3.14–3.06 (m, 1 H),
2.77–2.72 (m, 1 H), 2.64–2.28 (m, 3 H), 1.37 (d, J = 7.0 Hz, 3
H) ppm. 13C NMR (CDCl3, 50 MHz): δ = 173.3, 151.5, 129.4, 77.8,
49.6, 46.6, 28.2, 18.8 ppm. MS (EI): m/z (%) = 154 (6) [M]+, 112
(45), 67 (99). HRMS (EI): calcd. for C8H10O3 154.0630; found
154.0627. [α]2D5 = +78.5 (c = 1.0, CHCl3).
We thank the National Science Council of the Republic of China
for financial support of this program.
[1] For recent reviews of annonaceous acetogenins, see: a) F. Q.
Alali, X.-X. Liu, J. L. McLaughlin, J. Nat. Prod. 1999, 62, 504;
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Cortes, Phytochemistry 1998, 48, 1087; c) A. Cavé, B. Figadére,
A. Laurens, D. Cortes in Progress in the Chemistry of Organic
Natural Products: Acetogenins from Annonaceae (Ed.: W.
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X.-P. Fang, M. J. Rieser, Z.-M. Gu, G.-X. Zhao, J. L.
McLaughlin, Phytochem. Anal. 1993, 4, 27; e) A. Bermejo, B.
Figadére, M. C. Zafra-Polo, I. Barrachina, E. Estornell, D.
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(5S)-3-[(2R)-2-Hydroxy-5-(trimethylsilyl)pent-4-ynyl)-5-methyl-
furan-2(5H)-one (22): Prepared following the procedure used for
1
compound 17 in 80% yield as a pale yellow oil. H NMR (CDCl3,
400 MHz): δ = 7.22 (d, J = 1.4 Hz, 1 H), 5.05 (qd, J = 6.8, 1.4 Hz,
1 H), 4.05–3.93 (m, 1 H), 2.66–2.47 (m, 2 H), 2.44 (d, J = 6.0 Hz,
2 H), 1.42 (d, J = 7.0 Hz, 3 H), 0.14 (s, 9 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 174.4, 152.3, 130.4, 102.4, 78.0, 68.0, 31.9,
28.5, 19.0, 0.1 (3 C) ppm. MS (EI): m/z (%) = 237 (10) [M – 15]+,
141 (99), 73 (75). HRMS (EI): calcd. for C12H17O3Si 237.0947;
found 237.0949. [α]2D5 = +47.0 (c = 1.0, CHCl3).
[2] S. O. Jolad, J. J. Hoffmann, K. H. Schmarm, J. K. Cole, J. Org.
Chem. 1982, 47, 315.
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2003, 66, 279.
[5] a) J. L. Lee, C. F. Lin, L. Y. Hsieh, W. R. Lin, H. F. Chiu, Y. C.
Wu, K. S. Wang, M. J. Wu, Tetrahedron Lett. 2003, 44, 7833;
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S. R. Lin, Y. C. Wu, M. J. Wu, Bioorg. Med. Chem. 2005, 13,
5864; c) K. J. Quinn, A. K. Isaacs, A. B. DeChristopher, S. C.
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M. Higuchi, H. Konno, M. Murai, H. Miyoshi, Tetrahedron
Lett. 2005, 46, 4671.
(5S)-3-[(2R)-2-Hydroxypent-4-ynyl)-5-methylfuran-2(5H)-one (23):
Prepared following the procedure used for compound 4 in 80%
yield as a pale yellow oil. IR (neat): ν = 3432, 3288, 2974, 2148,
˜
1
1745 cm–1. H NMR (CDCl3, 200 MHz): δ = 7.24 (d, J = 1.6 Hz,
1 H), 5.04 (qd, J = 7.0, 1.6 Hz, 1 H), 4.08–3.96 (m, 1 H), 2.66–2.47
(m, 2 H), 2.39 (dd, J = 6.0, 2.6 Hz, 2 H), 2.07 (t, J = 2.6 Hz, 1 H),
1.42 (d, J = 7.0 Hz, 3 H) ppm. 13C NMR (CDCl3, 50 MHz): δ =
174.5, 152.5, 130.3, 80.1, 71.2, 67.8, 31.9, 27.0, 18.9 ppm. MS (EI):
m/z (%) = 180 (9) [M]+, 141 (99), 67 (99). HRMS (EI): calcd. for
C10H12O3 180.0786; found 180.0777. [α]2D5 = +45.0 (c = 1.0,
CHCl3).
[6] J. Gawronski, Y. C. Wu, Pol. J. Chem. 1999, 73, 241–243.
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(5S)-3-{(2S,13R)-2,13-Dihydroxy-13-[(5R)-2-oxo-4,5-dihydro-3H-fu-
ran-5-yl]trideca-4,6-diynyl}-5-methylfuran-2(5H)-one (24): Prepared
following the procedure used for compound 19 in 50% yield as a
[8] J. Wityak, J. B. Chan, Synth. Commun. 1991, 21, 977.
860
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Eur. J. Org. Chem. 2008, 854–861