Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2013; 24(10): 1303-1306
DOI: 10.1055/s-0033-1338447
DOI: 10.1055/s-0033-1338447
letter
Formal Synthesis of Aspidospermidine via the Intramolecular Cascade Transannular Cyclization
Further Information
Publication History
Received: 28 February 2013
Accepted after revision: 30 March 2013
Publication Date:
08 May 2013 (online)
Abstract
A formal synthesis of aspidospermidine is reported through a novel preparation of Stork’s penultimate tricyclic ketone intermediate. The key steps of the synthesis consist of an intramolecular cascade transannular cyclization, triggered by the removal of Boc group, which simultaneously forms the C, D, and E rings of aspidospermidine and conveniently setting up the quaternary stereocenter via decarboxylative alkylation reaction of the β-keto ester.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1 Saxton JE In The Alkaloids . Vol. 51. Cordell GA. Chap. 1 Academic Press; New York: 1998
- 2a Malawista SE, Sato H, Bensch KG. Science 1968; 160: 770
- 2b Gigant B, Wang CG, Ravelli RB. G, Roussi MO, Steinmetz PA, Curmi PA, Sobel A, Knossow M. Nature (London) 2005; 435: 519
- 3a Node M, Nagasawa H, Fuji K. J. Org. Chem. 1990; 55: 517
- 3b Schultz AG, Pettus L. J. Org. Chem. 1997; 62: 6855
- 3c Iyengar R, Schildknegt K, Aube J. Org. Lett. 2000; 2: 1625
- 3d Kozmin SA, Iwama T, Huang Y, Rawal VH. J. Am. Chem. Soc. 2002; 124: 4628
- 3e Marino JP, Rubio MB, Cao G, Dios A. J. Am. Chem. Soc. 2002; 124: 13398
- 3f Gnecco D, Vazquez E, Galindo A, Teran JL, Orea L, Bernes S, Enriquez RG. ARKIVOC 2003; (xi): 185
- 3g Iyengar R, Schildknegt K, Morton M, Aube J. J. Org. Chem. 2005; 70: 10645
- 3h Ishikawa T, Kudo K, Kuroyabu K, Uchida S, Kudoh T, Siato S. J. Org. Chem. 2008; 73: 7498
- 3i Suzuki M, Kawamoto Y, Sakai T, Yamamoto Y, Tomioka K. Org. Lett. 2009; 11: 653
- 3j Jones SB, Simmons B, Mastracchio A, MacMillan WC. Nature (London) 2011; 475: 183
- 4a Harley-Mason J, Kaplan M. Chem. Commun. 1967; 915
- 4b Kutney JP, Abdurahman N, Gletsos C, LeQuesne P, Piers E, Vlattas I. J. Am. Chem. Soc. 1970; 92: 1727
- 4c Wenkert E, Hudlicky T. J. Org. Chem. 1988; 53: 1953
- 4d Wenkert E, Liu S. J. Org. Chem. 1994; 59: 7677
- 4e Forns P, Diez A, Rubiralta M. J. Org. Chem. 1996; 61: 7882
- 4f Callaghan O, Lampard C, Kennedy AR, Murphy JA. Tetrahedron Lett. 1999; 40: 161
- 4g Callaghan O, Lampard C, Kennedy AR, Murphy JA. J. Chem. Soc., Perkin Trans. 1 1999; 8: 995
- 4h Toczko MA, Heathcock CH. J. Org. Chem. 2000; 65: 2642
- 4i Patro B, Murphy JA. Org. Lett. 2000; 2: 3599
- 4j Banwell MG, Smith JA. J. Chem. Soc., Perkin Trans. 1 2002; 2613
- 4k Banwell MG, Lupton DW. Org. Biomol. Chem. 2005; 3: 213
- 4l Banwell MG, Lupton DW, Willis AC. Aust. J. Chem. 2005; 58: 722
- 4m Sharp LA, Zard SZ. Org. Lett. 2006; 8: 831
- 4n Pearson WH, Aponick A. Org. Lett. 2006; 8: 1661
- 4o Coldham I, Burrell AJ. M, White JE, Adams H, Oram N. Angew. Chem. Int. Ed. 2007; 46: 6159
- 4p Callier-Dublanchet A.-C, Cassayre J, Gagosz F, Quiclet-Sire B, Sharp LA, Zard SZ. Tetrahedron 2008; 64: 4803
- 4q Ishikawa T, Kudo K, Kuroyabu K, Uchida S, Kudoh T, Saito S. J. Org. Chem. 2008; 73: 7498
- 4r Sabot C, Cuerard KC, Canesi S. Chem. Commun. 2009; 2941
- 4s De Simone F, Gertsch J, Waser J. Angew. Chem. Int. Ed. 2010; 49: 5767
- 4t Jiao L, Herdtweck E, Bach T. J. Am. Chem. Soc. 2012; 134: 14563
- 5 Stork G, Dolfini JE. J. Am. Chem. Soc. 1963; 85: 2872
- 6a Yang Y.-R, Shen L, Wei K, Zhao Q.-S. J. Org. Chem. 2010; 75: 1317
- 6b Yang Y.-R, Lai Z.-W, Shen L, Huang J.-Z, Wu X.-D, Yin J.-L, Wei K. Org. Lett. 2010; 12: 3430
- 6c Yang Y.-R, Shen L, Huang J.-Z, Xu Tao, Wei K. J. Org. Chem. 2011; 76: 3684
- 7 Behenna DC, Mohr JT, Sherden NH, Marinescu SC, Harned AM, Tani K, Seto M, Ma S, Novak Z, Krout MR, McFadden RM, Roizen JL, Enquist JA. Jr, White DE, Levine SR, Petrova KV, Iwashita A, Virgil SC, Stoltz BM. Chem. Eur. J. 2011; 17: 14199 ; and references cited therein
- 8 Miyaura N, Ishiyama T, Sasaki H, Ishikawa M, Satoh M, Suzuki A. J. Am. Chem. Soc. 1989; 111: 314
- 9 Paquette LA, Hu Y, Luxenburger A, Bishop RL. J. Org. Chem. 2007; 72: 209
- 10 Yamashita D, Murata Y, Hikage N, Takao K, Nakazaki A, Kobayashi S. Angew. Chem. Int. Ed. 2009; 48: 1404
- 11a Li H, Wang X, Hong B, Lei X. J. Org. Chem. 2013; 78: 800
- 11b Zhang X.-M, Shao H, Tu Y.-Q, Zhang F.-M, Wang S-H. J. Org. Chem. 2012; 77: 8174
- 12 Similar to the description by Banwell,4j we also found the ensuing Fischer indolization process was capricious when carried out on a small scale.
Syntheses of nonracemic aspidospermidine:
Syntheses of racemic aspidospermidine:
After we originally reported the discovery of this cascade cyclization,6a Tu and Lei also observed the similar cyclization in their total syntheses of lycojapodine A, see: