F
Y. Kurogome et al.
Paper
Synthesis
(6S,7R,2E)-6-(Benzyloxy)-7-hydroxydodec-2-enyl 2-Naphthoate (15)
IR (film): 3431, 2933, 2857, 1713, 1457, 1375, 1273, 1078, 1024, 988,
935 cm–1
.
This compound was synthesized as described in the synthesis of 6.
Compound 14 (721 mg, 2.61 mmol) and allyl 2-naphthoate (7) (2.7 g,
1H NMR (500 MHz, CDCl3): δ = 3.75–3.72 (m, 1 H), 3.26–3.25 (m, 1 H),
3.03 (dd, J = 9.0, 2.0 Hz, 1 H), 2.65 (dd, J = 15.0, 7.8 Hz, 1 H), 2.55–2.41
(m, 2 H), 2.38 (dd, J = 15.3, 4.8 Hz, 1 H), 2.10–2.06 (m, 1 H), 1.83–1.65
(m, 3 H), 1.51–1.20 (m, 9 H), 1.04 (t, J = 7.3 Hz, 3 H), 0.88 (t, J = 6.8 Hz,
3 H).
13C NMR (125 MHz, CDCl3): δ = 210.17, 82.10, 74.06, 70.41, 48.32,
37.04, 32.86, 31.89, 31.75, 31.21, 24.95, 22.58, 13.99, 7.46.
20
13 mmol) afforded 15 (1.13 g, 94%) as a colorless oil; [α]D –16.2 (c
1.11, CHCl3); E/Z = 10:1
IR (film): 3500, 3061, 3029, 2931, 2857, 1715, 1455, 1353, 1281,
1227, 1196, 1130, 1092, 960, 865, 826, 779, 762, 735, 698 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.61 (s, 1 H), 8.06 (dd, J = 8.5, 1.5 Hz, 1
H), 7.94 (d, J = 8.0 Hz, 1 H), 7.88 (d, J = 8.5 Hz, 2 H), 7.61–7.52 (m, 2 H),
7.35–7.26 (m, 5 H), 5.90–5.85 (m, 1 H), 5.75–5.70 (m, 1 H), 4.81 (d,
J = 6.0 Hz, 2 H), 4.62 (d, J = 11.5 Hz, 1 H), 4.52 (d, J = 11.0 Hz, 1 H),
3.86–3.84 (m, 1 H), 3.39–3.35 (m, 1 H), 2.40–2.20 (m, 1 H), 2.15–2.07
(m, 1 H), 2.06 (d, J = 2.5 Hz, 1 H), 1.78–1.74 (m, 1 H), 1.60–1.25 (m, 9
H), 0.88 (t, J = 6.8 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.54, 138.29, 136.04, 135.49,
132.46, 131.04, 129.33, 128.46, 128.20, 128.10, 127.88, 127.80,
127.74, 127.54, 126.60, 125.25, 124.42, 81.33, 71.79, 71.42, 65.73,
32.09, 31.89, 28.47, 27.65, 25.89, 22.59, 14.04.
HRMS-EI: m/z [M]+ calcd for C14H26O3; 242.1882, found: 242.1879.
Decytospolide B (2)
This compound was synthesized as described in the synthesis of 13.
Compound 1 (22 mg, 0.09 mmol) afforded 2 (22 mg, 84%) as a color-
less oil; [α]D20 +34.5 (c 1.11, CHCl3) {Lit.10 [α]D22 +21.9 (c 0.50, CHCl3)}.
IR (film): 2938, 2859, 1739, 1716, 1458, 1373, 1239, 1081, 1040, 940,
727 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 4.48–4.42 (m, 1 H), 3.79–3.75 (m, 1 H),
3.26–3.21 (m, 1 H), 2.67 (dd, J = 15.0, 8.0 Hz, 1 H), 2.55–2.42 (m, 2 H),
2.38 (dd, J = 15.3, 4.8 Hz, 1 H), 2.16–2.12 (m, 1 H), 2.04 (s, 3 H), 1.77–
1.72 (m, 1 H), 1.54–1.20 (m, 10 H), 1.04 (t, J = 7.3 Hz, 3 H), 0.87 (t,
J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 209.85, 170.29, 79.25, 74.15, 72.00,
48.14, 37.16, 31.87, 31.65, 30.75, 29.29, 24.77, 22.55, 13.97, 7.45.
HRMS-EI: m/z [M]+ calcd for C30H36O4; 460.2614, found: 460.2620.
(2R,3S,6R)-3-(Benzyloxy)-2-pentyl-6-vinyltetrahydropyran (16)
This compound was synthesized as described in the synthesis of 5.
Compound 15 (413 mg, 0.90 mmol) afforded 16 (238 mg, 92%) as a
colorless oil; [α]D20 +82.7 (c 1.98, CHCl3).
IR (film): 3088, 3065, 3030, 2932, 2859, 1496, 1455, 1435, 1353,
HRMS-EI: m/z [M]+ calcd for C16H28O4: 284.1988, found: 284.1992.
1292, 1205, 1099, 1082, 989, 921, 734, 697, 635 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.35–7.25 (m, 5 H), 5.86–5.81 (m, 1 H),
5.22 (dt, J = 17.5, 1.5 Hz, 1 H), 5.08 (d, J = 11.0 Hz, 1 H), 4.63 (d, J = 11.5
Hz, 1 H), 4.47 (d, J = 11.5 Hz, 1 H), 3.80–3.78 (m, 1 H), 3.25–3.22 (m, 1
H), 3.12–3.09 (m, 1 H), 2.29–2.25 (m, 1 H), 1.90–1.81 (m, 1 H), 1.79–
1.76 (m, 1 H), 1.52–1.25 (m, 9 H), 0.88 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 138.73, 138.51, 128.34, 127.76,
127.59, 114.71, 80.67, 77.51, 77.12, 70.93, 32.24, 32.07, 30.89, 29.28,
25.05, 22.67, 14.11.
Acknowledgement
This work was supported in part by JSPS KAKENHI Grant Number
24580160 to H.M. and 15J06154 to Y.K. We also thank JSPS for the
Young Science Research Fellowship to Y.K.
Supporting Information
HRMS-EI: m/z [M]+ calcd for C19H28O2; 288.2089, found: 288.2082.
Supporting information for this article is available online at
1-{(2R,5S,6R)-5-(Benzyloxy)-6-pentyltetrahydropyran-2-yl}butan-
2-one (17)
This compound was synthesized as described in the synthesis of 11.
Compound 16 (84 mg, 0.39 mmol) afforded 17 (62 mg, 64%, 4 steps)
as a colorless oil; [α]D20 +53.6 (c 0.99, CHCl3).
References
(1) For recent reviews of the synthesis of tetrahydropyrans:
(a) Makabe, H. Nat. Prod. Commun. 2013, 8, 1005. (b) Muzart, J.
J. Mol. Catal. A: Chem. 2010, 319, 1. (c) Muzart, J. Tetrahedron
2005, 61, 5955.
(2) Lu, S.; Sun, P.; Li, T.; Kurtán, R.; Mándi, A.; Antus, S.; Krohn, H.;
Draeger, S.; Schulz, B.; Li, Y.; Li, L.; Zhang, W. J. Org. Chem. 2011,
76, 9699.
(3) Reddy, P. J.; Reddy, A. S.; Yadav, J. S.; Reddy, B. V. S. Tetrahedron
Lett. 2012, 53, 4054.
(4) Krishna, P. R.; Nomula, R.; Ramana, D. V. Tetrahedron Lett. 2012,
53, 3612.
IR (film): 3030, 2932, 2858, 1715, 1496, 1455, 1411, 1375, 1348,
1205, 1083, 1027, 989, 736 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.35–7.25 (m, 5 H), 4.61 (d, J = 11.5 Hz,
1 H), 4.45 (d, J = 12.0 Hz, 1 H), 3.75–3.73 (m, 1 H), 3.08–3.04 (m, 1 H),
2.63 (dd, J = 15.0, 8.0 Hz, 1 H), 2.50–2.43 (m, 2 H), 2.36 (dd, J = 15.0,
5.0 Hz, 1 H), 2.24 (dd, J = 12.3, 3.8 Hz, 1 H), 1.87–1.75 (m, 3 H), 1.50–
1.20 (m, 9 H), 1.03 (t, J = 7.3 Hz, 3 H), 0.87 (t, J = 6.8 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 210.03, 138.43, 128.30, 127.71,
127.57, 80.76, 77.19, 74.09, 70.85, 48.39, 37.00, 32.07, 31.80, 29.14,
24.96, 22.62, 14.01, 7.45.
(5) Zeng, J.; Tan, Y. J.; Ma, J.; Leow, M. L.; Tirtorahardjo, D.; Liu, X.-
W. Chem. Eur. J. 2014, 20, 405.
HRMS-EI: m/z [M]+ calcd for C21H32O3; 332.2352, found: 332.2358.
(6) Clarisse, D.; Fache, F. Tetrahedron Lett. 2014, 55, 2221.
(7) Yahata, K.; Minami, M.; Watanabe, K.; Fujioka, H. Org. Lett. 2014,
16, 3680.
(8) Kammari, B. R.; Bejjanki, N. K.; Kommu, N. Tetrahedron: Asym-
metry 2015, 26, 296.
Decytospolide A (1)
This compound was synthesized as described in the synthesis of 12.
Compound 17 (60 mg, 0.18 mmol) afforded 1 (44 mg, quant.) as a col-
orless oil; [α]D19 +23.8 (c 1.01, CHCl3) {Lit.10 [α]D22 +15.3 (c 0.500, CH-
Cl3)}.
(9) Srilatha, M.; Das, B. Helv. Chim. Acta 2015, 98, 267.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–G