Total Synthesis of (+)-Neopeltolide†
Haruhiko Fuwa Dr.
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorShinya Naito
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorTomomi Goto
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorMakoto Sasaki Prof. Dr.
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorHaruhiko Fuwa Dr.
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorShinya Naito
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorTomomi Goto
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorMakoto Sasaki Prof. Dr.
Laboratory of Biostructural Chemistry, Graduate School of Life Sciences, Tohoku University, 1-1 Tsutsumidori-amamiya, Aoba-ku, Sendai 981-8555, Japan, Fax: (+81) 22-717-8896
Search for more papers by this authorThis work was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Sports, Culture, Science and Technology (Japan).
Graphical Abstract
Rapid elaboration: (+)-Neopeltolide, a novel marine metabolite with potent cytotoxicity against several cancer cell lines, was the target of an efficient total synthesis (see scheme). The construction of the 2,4,6-trisubstituted tetrahydropyran substructure is based on a Suzuki–Miyaura coupling/ring-closing metathesis sequence. BOM=benzyloxymethyl, MPM=4-methoxyphenylmethyl, TIPS=triisopropylsilyl.
Supporting Information
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References
- 1A. E. Wright, J. C. Botelho, E. Guzmán, D. Harmody, P. Linley, P. J. McCarthy, T. P. Pitts, S. A. Pomponi, J. K. Reed, J. Nat. Prod. 2007, 70, 412.
- 2W. Youngsaye, J. T. Lowe, F. Pohlki, P. Falifo, J. S. Panek, Angew. Chem. 2007, 119, 9371;
10.1002/ange.200704122 Google ScholarAngew. Chem. Int. Ed. 2007, 46, 9211.
- 3D. W. Custer, T. P. Zabawa, K. A. Scheidt, J. Am. Chem. Soc. 2008, 130, 804.
- 4V. V. Vintonyak, M. E. Maier, Org. Lett. 2008, 10, 1239.
- 5S. K. Woo, M. S. Kwon, E. Lee, Angew. Chem. 2008, 120, 3286; Angew. Chem. Int. Ed. 2008, 47, 3242.
- 6For reviews of Suzuki–Miyaura coupling, see:
- 6aN. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457;
- 6bS. R. Chemler, D. Trauner, S. J. Danishefsky, Angew. Chem. 2001, 113, 4676;
10.1002/1521-3757(20011217)113:24<4676::AID-ANGE4676>3.0.CO;2-B Google ScholarAngew. Chem. Int. Ed. 2001, 40, 4544.10.1002/1521-3773(20011217)40:24<4544::AID-ANIE4544>3.0.CO;2-N CAS PubMed Web of Science® Google Scholar
- 7For reviews of ring-closing metathesis, see:
- 7aA. Fürstner, Angew. Chem. 2000, 112, 3140;
10.1002/1521-3757(20000901)112:17<3140::AID-ANGE3140>3.0.CO;2-G Google ScholarAngew. Chem. Int. Ed. 2000, 39, 3012;10.1002/1521-3773(20000901)39:17<3012::AID-ANIE3012>3.0.CO;2-G CAS PubMed Web of Science® Google Scholar
- 7bK. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. 2005, 117, 4564;
10.1002/ange.200500369 Google ScholarAngew. Chem. Int. Ed. 2005, 44, 4490.
- 8O. Mitsunobu, Synthesis 1981, 1.
- 9Y. Yang, J. Janjic, S. A. Kozmin, J. Am. Chem. Soc. 2002, 124, 13670.
- 10J. Inanaga, K. Hirata, H. Saeki, T. Katsuki, M. Yamaguchi, Bull. Chem. Soc. Jpn. 1979, 52, 1989.
- 11For our successful implementation of enol phosphates in palladium-catalyzed synthesis of heterocycles, see:
- 11aM. Sasaki, H. Fuwa, M. Ishikawa, K. Tachibana, Org. Lett. 1999, 1, 1075;
- 11bM. Sasaki, M. Ishikawa, H. Fuwa, K. Tachibana, Tetrahedron 2002, 58, 1889;
- 11cH. Fuwa, N. Kainuma, K. Tachibana, M. Sasaki, J. Am. Chem. Soc. 2002, 124, 14983;
- 11dC. Tsukano, M. Ebine, M. Sasaki, J. Am. Chem. Soc. 2005, 127, 4326;
- 11eH. Fuwa, M. Ebine, A. J. Bourdelais, D. G. Baden, M. Sasaki, J. Am. Chem. Soc. 2006, 128, 16989;
- 11fH. Fuwa, A. Kaneko, Y. Sugimoto, T. Tomita, T. Iwatsubo, M. Sasaki, Heterocycles 2006, 70, 101;
- 11gH. Fuwa, M. Sasaki, Org. Biomol. Chem. 2007, 5, 1849;
- 11hH. Fuwa, M. Sasaki, Chem. Commun. 2007, 2876;
- 11iH. Fuwa, M. Sasaki, Org. Lett. 2007, 9, 3347.
- 12For other examples of the synthesis of endocyclic enol ethers employing RCM, see:
- 12aK. C. Nicolaou, M. H. D. Postema, C. F. Claiborne, J. Am. Chem. Soc. 1996, 118, 1565;
- 12bJ. D. Rainier, S. P. Allwein, J. Org. Chem. 1998, 63, 5310;
- 12cD. Calimente, M. H. D. Postema, J. Org. Chem. 1999, 64, 1770;
- 12dJ. S. Clark, M. C. Kimber, J. Robertson, C. S. P. McErlean, C. Wilson, Angew. Chem. 2005, 117, 6313; Angew. Chem. Int. Ed. 2005, 44, 6157.
- 13H. C. Brown, P. K. Jadhav, J. Am. Chem. Soc. 1981, 105, 2092.
- 14For a review of olefin cross-metathesis, see: S. J. Connon, S. Blechert, Angew. Chem. 2003, 115, 1944;
10.1002/ange.200200556 Google ScholarAngew. Chem. Int. Ed. 2003, 42, 1900.
- 15F. Keyling-Bilger, G. Schimitt, A. Beck, B. Luu, Tetrahedron 1996, 52, 14891.
- 16Treatment of lactone 25 with KHMDS or LHMDS resulted in decomposition of the starting material, even in the presence of (PhO)2P(O)Cl, PhNTf2, or Comins reagent (2-[N,N-bis(trifluoromethylsulfonyl)amino]-5-chloropyridine).
- 17E. D. Laganis, B. L. Chenard, Tetrahedron Lett. 1984, 25, 5831.
