F
Synthesis
Z. Li, R. Tong
Special Topic
tracted with CH Cl (3 × 5 mL). The combined organic fractions were
Aust. J. Chem. 1995, 48, 199. (c) Mu, Q.; Tangm, W.; Li, C.; Lu, Y.;
Sun, H.; Zheng, H.; Hao, X.; Zheng, Q.; Wu, N.; Lou, L.; Xu, B. Het-
erocycles 1999, 51, 2969.
2
2
washed with brine, dried (MgSO ), and concentrated under reduced
4
pressure. The residue was purified by flash column chromatography
on silica gel using eluents (EtOAc/hexane, 1:2 → 1:1) to give (+)-dio-
spongin B (1b) (11.3 mg, 0.037 mmol, 62% yield over three steps) as a
(7) Jennings, M. P.; Sawant, K. B. J. Org. Chem. 2006, 71, 7911.
(8) Kawai, N.; Hande, S.-M.; Uenishi, J. Tetrahedron 2007, 63, 9049.
(9) Sabitha, G.; Padmaja, P. Helv. Chim. Acta 2008, 91, 2235.
(10) Wang, H.; Shuhler, B. J.; Xian, M. Synlett 2008, 2651.
20
white foam; [α]D +25.3 (c 0.52, CHCl3).
IR (neat): 3426, 2930, 1693, 1603, 1487, 1460, 1063 cm–1
.
(
11) Kumaraswamy, G.; Ramakrishna, G.; Naresh, P.; Jagadeesh, B.;
1
H NMR (400 MHz, CDCl ): δ = 8.01–7.94 (m, 2 H), 7.62–7.55 (m, 1 H),
3
Sridhar, B. J. Org. Chem. 2009, 74, 8468.
7
4
1
.51–7.44 (m, 2 H), 7.37–7.31 (m, 4 H), 7.25–7.19 (m, 1 H), 5.19 (t, J =
.3 Hz, 1 H), 4.23 (ddt, J = 9.2, 6.6, 3.4 Hz, 1 H), 4.02 (tt, J = 9.2, 4.2 Hz,
H), 3.45 (dd, J = 15.7, 7.2 Hz, 1 H), 3.17 (dd, J = 15.8, 6.0 Hz, 1 H), 2.52
(
(
12) Stefan, E.; Nalin, A. P.; Taylor, R. E. Tetrahedron 2013, 69, 7706.
13) Anada, M.; Washio, T.; Watanabe, Y.; Takeda, K.; Hashimoto, S.
Eur. J. Org. Chem. 2010, 6850.
14) Rybak, T.; Hall, D. G. Org. Lett. 2015, 17, 4156.
15) Yang, Z.-C.; Zhou, W.-S. Chin. J. Chem. 1996, 14, 152.
(16) Friesen, R. W.; Bissada, S. Can. J. Chem. 1998, 76, 94.
(17) Kumaraswamny, G.; Kumar, R. S. Helv. Chim. Acta 2013, 96,
1366.
(dtd, J = 13.4, 3.8, 1.7 Hz, 1 H), 2.11–2.01 (m, 1 H), 1.92 (ddd, J = 13.4,
(
(
9.8, 5.2 Hz, 1 H), 1.73 (br s, 1 H), 1.51 (dt, J = 12.6, 9.5 Hz, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 198.5, 140.4, 137.3, 133.3, 128.8 (2 ×
3
C), 128.7 (2 × C), 128.4 (2 × C), 127.2, 126.5 (2 × C), 72.5, 67.1, 64.3,
44.8, 40.3, 36.9.
+
+
(18) Mukai, C.; Hirai, S.; Hanaoka, M. J. Org. Chem. 1997, 62, 6619.
HRMS (TOF, CI ): m/z [M + H] calcd for C19H21O : 297.1491; found:
3
(19) Prasad, K. R.; Dhaware, M. G. Synlett 2007, 1112.
297.1501.
(20) Ramachandran, P. V.; Chandra, J. S.; Reddy, M. V. R. J. Org. Chem.
2002, 67, 7547.
(
(
21) Survivet, J.-P.; Vatèle, J.-M. Tetrahedron 1999, 55, 13011.
22) Yamashita, Y.; Saito, S.; Ishitani, H.; Kobayashi, S. J. Am. Chem.
Soc. 2003, 125, 3793.
Acknowledgment
This research was financially supported by HKUST (R9309), Research
Grant Council of Hong Kong (GRF 605113, 16305314), and the Na-
tional Natural Science Foundation of China (NSFC 21472160). The au-
thors also acknowledge Dr. Herman (HKUST) and Prof. Williams
(23) (a) Surivet, J.-P.; Vatèle, J.-M. Tetrahedron Lett. 1998, 39, 9681.
(
b) Surivet, J.-P.; Vatèle, J.-M. Tetrahedron 1999, 55, 13011.
24) For a recent review, see: Nising, C. F.; Bräse, S. Chem. Soc. Rev.
008, 37, 1218.
(
2
(HKUST) for the X-ray diffraction analysis and thank HKUST under-
(
(
25) Li, Z.; Tong, R. Chem. Eur. J. 2015, 21, 11152.
26) For selected examples, see: (a) Hashiguchi, S.; Fujii, A.; Takehara,
K.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 7562.
graduates MAK, Chun Him (Abel), TANG, and Wai Sum for the prepa-
ration of some starting materials.
(b) Fujii, A.; Hashiguchi, S.; Uematsu, N.; Ikariya, T.; Noyori, R.
J. Am. Chem. Soc. 1996, 118, 2521. (c) Ferrie, L.; Reymond, S.;
Capdevielle, P.; Cossy, J. Org. Lett. 2007, 9, 2461. (d) Zhu, L.; Liu,
Y.; Ma, R.; Tong, R. Angew. Chem. Int. Ed. 2015, 54, 627. For a
review, see: (e) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997,
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1561592.
S
u
p
p
ortioIgnfrm oaitn
S
u
p
p
ortioIgnfrm oaitn
30, 97.
(
27) (a) Achmatowicz, O. Jr.; Bukowski, P.; Szechner, B.;
References
Zwierzchowska, Z.; Zamojski, A. Tetrahedron 1971, 27, 1973.
(b) Georgiadis, M. P.; Couladouros, E. A. J. Org. Chem. 1986, 51,
(1) For recent reviews on THP synthesis, see: (a) Clarke, P. A.;
2725.
Santos, S. Eur. J. Org. Chem. 2006, 2045. (b) Nasir, N. M.; Ermanis,
K.; Clarke, P. A. Org. Biomol. Chem. 2014, 12, 3323. (c) Larrosa, I.;
Romea, P.; Urpi, F. Tetrahedron 2008, 64, 2683.
(
28) Plietker, B.; Niggemann, M. J. Org. Chem. 2004, 70, 2402.
29) (a) Hutchins, R. O.; Milewski, C. A.; Maryanoff, B. E. J. Am. Chem.
Soc. 1973, 95, 3662. (b) Kabalka, G. W.; Baker, J. D. Jr. J. Org.
Chem. 1975, 40, 1834. (c) Hanessian, S.; Faucher, A.-M. J. Org.
Chem. 1991, 56, 2947. (d) Thompson, C. F.; Jamison, T. F.;
Jacobsen, E. N. J. Am. Chem. Soc. 2000, 122, 10482. (e) Ghosh, A.
K.; Li, J. Org. Lett. 2009, 11, 4164.
(
(
2) For selected natural products such as calyxins, polycarcin V,
musellarins, katsumain D, and hedycoropyran A, see: (a) Tian,
X.; Jaber, J. J.; Rychnovsky, S. D. J. Org. Chem. 2006, 71, 3176.
(b) Cai, X.; Panesar, H.; Moon, S.-J.; Paredes, M.; Ishida, K.;
Hertweck, C.; Minehan, T. G. Org. Lett. 2014, 16, 2962. (c) Li, Z.;
Leung, T.-F.; Tong, R. Chem. Commun. 2014, 50, 10990. (d) Nam,
J.-W.; Seo, E.-K. Helv. Chim. Acta 2013, 96, 1670. (e) Lin, Y.-S.;
Lin, J.-H.; Chang, C.-H.; Lee, S.-S. J. Nat. Prod. 2015, 78, 181.
3) Yin, J.; Kouda, K.; Tezuka, Y.; Le Tran, Q.; Miyahara, T.; Chen, Y.;
Kadota, S. Planta Med. 2004, 70, 54.
4) Liou, J.-R.; Wu, T.-Y.; Thang, T. D.; Hwang, T.-L.; Wu, C.-C.;
Cheng, Y.-B.; Chiang, M. Y.; Lan, Y.-H.; El-Shazly, M.; Wu, S.-L.;
Beerhues, L.; Yuan, S.-S.; Hou, M.-F.; Chen, S.-L.; Chang, F.-R.;
Wu, Y.-C. J. Nat. Prod. 2014, 77, 2626.
(
(
30) Dess, D. B.; Martin, J. C. J. Org. Chem. 1983, 48, 4155.
31) Bal, B. S.; Childers, W. E.; Pinnick, H. W. Tetrahedron 1981, 37,
2091.
(
32) For recent total synthesis of leiocarpin A, see: (a) Chen, J.; Lin,
G.-Q.; Liu, H.-Q. Tetrahedron Lett. 2004, 45, 8111. (b) Nagaiah,
K.; Sreenu, D.; Purnima, K. V.; Rao, R. S.; Yadav, J. S. Synthesis
(
(
2009, 1386. (c) For X-ray crystal structure data, see ref. 6.
(33) Swamy, K. C.; Kumar, N. N.; Balaraman, E.; Kumar, K. V. Chem.
Rev. 2009, 109, 2551.
(34) Tidwell, T. T. Synthesis 1990, 857.
(5) Fang, X. P.; Anderson, J. E.; Chang, C. J.; McLaughlin, J. L.;
Fanwick, P. E. J. Nat. Prod. 1991, 54, 1034.
(35) Ley, S. V.; Norman, J.; Griffith, W. P.; Marsden, S. P. Synthesis
1994, 639.
(6) (a) Tai, B. H.; Huyen, V. T.; Huong, T. T.; Nhiem, N. X.; Choi, E. M.;
Kim, J. A.; Long, P. Q.; Cuong, N. M.; Kim, Y. H. Chem. Pharm. Bull.
(36) Bowden, K.; Heilbron, I. M.; Jones, E. R. H.; Weedon, B. C. L.
J. Chem. Soc. 1946, 39.
2010, 58, 521. (b) Goh, S. H.; Ee, G. C. L.; Chuah, C. H.; Wei, C.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–G