Synlett, Table of Contents Synlett 2012; 23(14): 2014-2024DOI: 10.1055/s-0032-1316680 account © Georg Thieme Verlag Stuttgart · New YorkSyntheses of Fawcettimine-Type Lycopodium Alkaloids Utilizing the Pauson–Khand Reaction Authors Author Affiliations Atsushi Nakayama Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan, Fax: +81(43)2262914 Email: htakayam@p.chiba-u.ac.jp Mariko Kitajima Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan, Fax: +81(43)2262914 Email: htakayam@p.chiba-u.ac.jp Hiromitsu Takayama* Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan, Fax: +81(43)2262914 Email: htakayam@p.chiba-u.ac.jp Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract The asymmetric total syntheses of some fawcettimine-type Lycopodium alkaloids, utilizing an intramolecular Pauson–Khand reaction as the key step, are described. 1 Introduction 2 First Asymmetric Total Syntheses of Lycoposerramine-C and Phlegmariurine A 3 First Asymmetric Total Synthesis of Huperzine Q 4 Total Syntheses of Fawcettimine and Fawcettidine 5 Conclusion Key words Key wordsalkaloids - total synthesis - asymmetric synthesis - fawcettimine - Pauson–Khand reaction Full Text References References For recent reviews, see: 1a Kitajima M, Takayama H. Topics in Current Chemistry. Vol. 309. Knölker H.-J. Springer; Berlin: 2012: 1-31 1b Hirasawa Y, Kobayashi J, Morita H. Heterocycles 2009; 77: 679 1c Kobayashi J, Morita H. The Alkaloids . Vol. 61. Cordell GA. Academic; New York: 2005: 1-57 1d Ayer WA, Trifonov LS. The Alkaloids . Vol. 45. Cordell GA, Brossi A. Academic; New York: 1994: 233 1e Ma X, Gang DR. Nat. Prod. Rep. 2004; 21: 752 2a Liu L.-S, Zhu Y.-L, Yu C.-M, Zhou Y.-Z, Han Y.-Y, Wu F.-W, Qi B.-F. Can. J. Chem. 1986; 64: 837 2b Kozikowski AP, Tückmantel W. Acc. Chem. Res. 1999; 32: 641 ; and references cited therein 3a Hirasawa Y, Kobayashi J, Obara Y, Nakahata N, Kawahara N, Goda Y, Morita H. Heterocycles 2006; 68: 2357 3b Hirasawa Y, Morita H, Kobayashi J. Org. Lett. 2004; 6: 3389 3c Kobayashi J, Hirasawa Y, Yoshida N, Morita H. J. Org. Chem. 2001; 66: 5901 3d Kobayashi J, Hirasawa Y, Yoshida N, Morita H. Tetrahedron Lett. 2000; 41: 9069 3e Ishiuchi K, Kubota T, Hoshino T, Obara Y, Nakahata N, Kobayashi J. Bioorg. Med. Chem. 2006; 14: 5995 For selected recent total syntheses of Lycopodium alkaloids, see: 4a Zhang X.-M, Tu Y.-Q, Zhang F.-M, Shao H, Meng X. Angew. Chem. Int. Ed. 2011; 50: 3916 4b Nishimura T, Unni AK, Yokoshima S, Fukuyama T. J. Am. Chem. Soc. 2011; 133: 418 4c Canham SM, France DJ, Overman LE. J. Am. Chem. Soc. 2010; 132: 7876 4d Yuan C, Chang C, Axelrod A. Siegel D. 2010; 132: 5924 4e Fischer DF, Sarpong R. J. Am. Chem. Soc. 2010; 132: 5926 4f Liau BB, Shair MD. J. Am. Chem. Soc. 2010; 132: 9594 4g Ramharyer J, Weinstabl H, Mulzer J. J. Am. Chem. Soc. 2010; 132: 14338 4h Bisai V, Sarpong R. Org. Lett. 2010; 12: 2551 4i Yang H, Carter RG. J. Org. Chem. 2010; 75: 4929 4j Chandra A, Pigza JA, Han J.-S, Mutnick D, Johnston JN. J. Am. Chem. Soc. 2009; 131: 3470 4k Nishikawa Y, Kitajima M, Kogure N, Takayama H. Tetrahedron 2009; 65: 1608 4l Tanaka T, Kogure N, Kitajima M, Takayama H. J. Org. Chem. 2009; 74: 8675 Lycoposerramine-A: 5a Takayama H, Katakawa K, Kitajima M, Seki H, Aimi N. Org. Lett. 2001; 3: 4165 , Org. Lett. 2002, 4, 1243 Lycoposerramine-B: 5b Katakawa K, Kitajima M, Aimi N, Seki H, Yamaguchi K, Furihata K, Harayama T, Takayama H. J. Org. Chem. 2005; 70: 658 5c Sieboldine A, Hirasawa Y, Morita H, Shiro M, Kobayashi J. Org. Lett. 2003; 5: 3991 For selected recent isolations, see: 5d Ishiuchi K, Kubota T, Ishiyama H, Hayashi S, Shibata T, Kobayashi J. Tetrahedron Lett. 2011; 52: 289 5e Ishiuchi K, Kubota T, Ishiyama H, Hayashi S, Shibata T, Mori T, Obara K, Nakahata Y, Nakahata N, Kobayashi J. Bioorg. Med. Chem. 2011; 19: 749 5f Hirasawa Y, Astulla A, Shiro M, Morita H. Tetrahedron Lett. 2011; 52: 4126 5g Katakawa K, Mito H, Kogure N, Kitajima M, Wongseripipatana S, Arisawa M, Takayama H. Tetrahedron 2011; 67: 6561 5h Zhao F.-W, Sun Q.-Y, Yang F.-M, Guang W, Luo J.-F, Tang G.-H, Wang Y.-H, Long C.-L. Org. Lett. 2010; 12: 3922 6 Burnell RH. J. Chem. Soc. 1959; 3091 7a Harayama T, Takatani M, Inubushi Y. Tetrahedron Lett. 1979; 20: 4307 7b Harayama T, Takatani M, Inubushi Y. Chem. Pharm. Bull. 1980; 28: 2394 8a Heathcock CH, Smith KM, Blumenkopf TA. J. Am. Chem. Soc. 1986; 108: 5022 8b Heathcock CH, Blumenkopf TA, Smith KM. J. Org. Chem. 1989; 54: 1548 9 Linhu X, Kennedy-Smith JJ, Toste FD. Angew. Chem. Int. Ed. 2007; 46: 7671 10a Liu K, Chau C, Sha C. Chem. Commun. (Cambridge) 2008; 91 10b Otsuka Y, Inagaki F, Mukai C. J. Org. Chem. 2010; 75: 3420 10c Jung ME, Chang JJ. Org. Lett. 2010; 12: 2962 10d Yang Y, Shen L, Huang J, Xu T, Wei K. J. Org. Chem. 2011; 76: 3684 10e Guojun P, Williams RM. J. Org. Chem. 2012; 77: 4801 11a Cassayre J, Gagosz F, Zard SZ. Angew. Chem. Int. Ed. 2002; 41: 1783 11b Ishizaki M, Niimi Y, Hoshino O, Hara H, Takahashi T. Tetrahedron 2005; 61: 4053 11c Kozaka T, Miyakoshi N, Mukai C. J. Org. Chem. 2007; 72: 10147 11d See also ref. 10b. 12 Takayama H, Katakawa K, Kitajima M, Yamaguchi K, Aimi N. Tetrahedron Lett. 2002; 43: 8307 13a Wu M, Yeh J. Tetrahedron 1994; 50: 1073 13b Williams DR, Mullins RJ, Miller NA. Chem. Commun. (Cambridge) 2003; 2220 14a Corey EJ, Bakshi RK, Shibata S. J. Am. Chem. Soc. 1987; 109: 5551 14b Parker KA, Ledeboer MW. J. Org. Chem. 1996; 61: 3214 15a Khand IU, Knox GR, Pauson PL, Watts WE. J. Chem. Soc. D 1971; 36: 36 15b Schore NE, Croudace MC. J. Org. Chem. 1981; 46: 5436 15c Shambayati S, Crowe WE, Schreiber SL. Tetrahedron Lett. 1990; 31: 5289 15d Jeong N, Chung YK, Lee SH, Yoo S.-E. Synlett 1991; 204 16a Mandai T, Ueda M, Hasegawa S, Kawada M, Tsuji J. Tetrahedron Lett. 1990; 31: 4041 16b Kaliappan KP, Ravikumar V. Org. Lett. 2007; 9: 2417 17a Fukuyama T, Jow C.-K, Cheung M. Tetrahedron Lett. 1995; 36: 6373 17b Kurosawa W, Kan T, Fukuyama T. Org. Synth. 2002; 79: 186 17c Kan T, Fukuyama T. Chem. Commun. (Cambridge) 2004; 353 18 Itoh Y, Hirao T, Saegusa T. J. Org. Chem. 1978; 43: 1011 19 Nakayama A, Kogure N, Kitajima M, Takayama H. Org. Lett. 2009; 11: 5554 20 Tan C.-H, Ma X.-Q, Chen G.-F, Zhu D.-Y. Helv. Chim. Acta 2002; 85: 1058 21a Noyori R, Hashiguchi S. Acc. Chem. Res. 1997; 30: 97 21b Matsumura K, Hashiguchi S, Ikariya T, Noyori R. J. Am. Chem. Soc. 1997; 119: 8738 21c Haack KJ, Hashiguchi S, Fujii A, Ikariya T, Noyori R. Angew. Chem., Int. Ed. Engl. 1997; 36: 285 22 Li B, Buzon RA, Castaldi MJ. Org. Process Res. Dev. 2001; 5: 609 23 Tang Y, Deng L, Zhang Y, Dong G, Chen J, Yang Z. Org. Lett. 2005; 7: 593 24 Hanessian S, Delorme D, Dufresne Y. Tetrahedron Lett. 1984; 25: 2515 25 Ishihara K, Kurihara H, Yamamoto H. J. Org. Chem. 1993; 58: 3791 26 Nakayama A, Kogure N, Kitajima M, Takayama H. Angew. Chem. Int. Ed. 2011; 50: 8025
