Synlett 2015; 26(11): 1505-1509
DOI: 10.1055/s-0034-1380685
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of (+)-Methyl Dihydropalustramate and of the Pyrido[1,2-a]azepine Core of Stemona Alkaloids

Camilla Mayer
Department Chemie and Catalysis Research Center (CRC), Technische Universität München, 85747 Garching, Germany   Email: thorsten.bach@ch.tum.de
,
Alexandra Romek
Department Chemie and Catalysis Research Center (CRC), Technische Universität München, 85747 Garching, Germany   Email: thorsten.bach@ch.tum.de
,
Thorsten Bach*
Department Chemie and Catalysis Research Center (CRC), Technische Universität München, 85747 Garching, Germany   Email: thorsten.bach@ch.tum.de
› Author Affiliations
Further Information

Publication History

Received: 05 March 2015

Accepted after revision: 09 April 2015

Publication Date:
30 April 2015 (online)


Dedicated to Professor K. Peter C. Vollhardt

Abstract

Starting from a readily available, enantiomerically pure 2,6-disubstituted piperidine the synthesis of pyrido[1,2-a]azepines was accomplished. Key reactions for the ring closure were a photochemically induced acyl radical addition or a SmI2-promoted ketyl radical addition to an α,β-unsaturated ester. En route to the cyclization precursor an epoxidiation/ring opening sequence led to an undesired oxazolidinone which turned out to be useful for the configuration assignment. The compound was successfully converted into (+)-methyl dihydropalustramate.

Supporting Information

Primary Data

 
  • References and Notes

  • 1 For a review, see: Alibés R, Figueredo M. Eur. J. Org. Chem. 2009; 2421

    • For recently completed total syntheses, see:
    • 2a Hoye AT, Wipf P. Org. Lett. 2011; 13: 2634
    • 2b Honda T, Matsukawa T, Takahashi K. Org. Biomol. Chem. 2011; 9: 673
    • 2c Chen Z, Chen Z, Zhang Y, Tu Y, Zhang F. J. Org. Chem. 2011; 76: 10173
    • 2d Chen Z, Zhang Y, Chen Z, Tu Y, Zhang F. Chem. Commun. 2011; 47: 1836
    • 2e Fujioka H, Nakahara K, Kotoku N, Ohba Y, Nagatomi Y, Wang T, Sawama Y, Murai K, Hirano K, Oki T, Wakamatsu S, Kita Y. Chem. Eur. J. 2012; 18: 13861
    • 2f Bardaji N, Sánchez-Izquierdo N, Alibés R, Font J, Busqué F, Figueredo M. Org. Lett. 2012; 14: 4854
    • 2g Swamy NK, Pyne SG. Heterocycles 2012; 84: 473
    • 2h Schulte ML, Turlington ML, Phatak SS, Harp JM, Stauffer SR, Lindsley CW. Chem. Eur. J. 2013; 19: 11847
    • 2i Kim C, Kang S, Rhee YH. J. Org. Chem. 2014; 79: 11119
    • 2j Fu J, Shen H, Chang Y, Li C, Gong J, Yang Z. Chem. Eur. J. 2014; 20: 12881

      For reviews, see:
    • 3a Pyne SG, Ung AT, Jatisatienr A, Mungkornasawakul P. Mj. Int. J. Sci. Tech. 2007; 01: 157
    • 3b Fischer G. Adv. Heterocycl. Chem. 2011; 103: 61
  • 5 Pilli RA, Rosso GB, de Oliveira MC. F. Alkaloids Chem. Biol. 2005; 62: 77

    • For examples, see:
    • 6a Kaltenegger E, Brem B, Mereiter K, Kalchhauser H, Kählig H, Hofer O, Vajrodaya S, Greger H. Phytochemistry 2003; 63: 803
    • 6b Mungkornasawakul P, Pyne SG, Jatisatienr A, Supyen D, Lie W, Ung AT, Skelton BW, White AH. J. Nat. Prod. 2003; 66: 980
    • 6c Mungkornasawakul P, Pyne SG, Jatisatienr A, Supyen D, Jatisatienr C, Lie W, Ung AT, Skelton BW, White AH. J. Nat. Prod. 2004; 67: 675
    • 6d Lin L.-G, Tang C.-P, Dien P.-H, Xu R.-S, Ye Y. Tetrahedron Lett. 2007; 48: 1559
    • 6e Wang Y.-Z, Tang C.-P, Dien P.-H, Ye Y. J. Nat. Prod. 2007; 70: 1356

      For previous synthetic studies, see:
    • 7a Fozard A, Jones G. J. Org. Chem. 1965; 30: 1523
    • 7b Tietze LF, Wünsch JR, Noltemeyer M. Tetrahedron 1992; 48: 2081
    • 7c Marx K, Eberbach W. Tetrahedron 1997; 53: 14687
    • 7d Chou S.-SP, Liang C.-F, Lee T.-M, Liu C.-F. Tetrahedron 2007; 63: 8267
    • 7e De la Funeta MC, Dominguez D. J. Org. Chem. 2007; 72: 8804
    • 7f Chaiyong S, Jatisatienr A, Mungkornasawakul P, Sastraruji T, Pyne SG, Ung AT, Urathamakul T, Lie W. J. Nat. Prod. 2010; 73: 1833
    • 7g Shengule SR, Willis AC, Pyne SG. Tetrahedron 2013; 69: 8042
    • 8a Chênevert R, Dickman M. J. Org. Chem. 1996; 61: 3332
    • 8b Chênevert R, Ziarani GM, Morin MP, Dasser M. Tetrahedron: Asymmetry 1999; 10: 3117
    • 9a Paulsen H, Todt K. Angew. Chem. Int. Ed. 1966; 5: 899
    • 9b Sugg EE, Griffin JF, Portoghese PS. J. Org. Chem. 1985; 50: 5032
    • 10a Toyooka N, Zhou D, Nemoto H, Tezuka Y, Kadota S, Jones TH, Garraffo HM, Spande TF, Daly JW. Synlett 2008; 1894
    • 10b See also: Ookawa A, Soai K. J. Chem. Soc., Perkin Trans. 1 1987; 1465
    • 11a Murray RW, Jeyaraman R. J. Org. Chem. 1985; 50: 2847
    • 11b Murray RW, Singh M. Org. Synth. 1997; 74: 91
    • 11c Bach RD, Dmitrenko O, Adam W, Schambony S. J. Am. Chem. Soc. 2003; 125: 924
    • 12a Gilman H, Jones RG, Woods LA. J. Org. Chem. 1952; 17: 1630
    • 12b Badorrey R, Porteña E, Diaz-de-Villegas MD, Galvez JA. Org. Biomol. Chem. 2009; 7: 2912
    • 13a Omura K, Swern D. Tetrahedron 1978; 34: 1651
    • 13b Lesma G, Colombo A, Landoni N, Sacchetti A, Silvani A. Tetrahedron: Asymmetry 2007; 18: 1948
    • 14a Nader B, Bailey TR, Franck RW, Weinreb SM. J. Am. Chem. Soc. 1981; 103: 7573
    • 14b Angle SR, Henry RM. J. Org. Chem. 1998; 63: 7490
    • 14c Schützenmeister N, Müller M, Reinscheid UM, Griesinger C, Leonov A. Chem. Eur. J. 2013; 19: 17584
    • 15a Seyferth D, Marmor RS, Hilbert P. J. Org. Chem. 1971; 36: 1379
    • 15b Gilbert JC, Weerasooriya U. J. Org. Chem. 1979; 44: 4997
    • 15c Maehr H, Schaffner C. Synth. Commun. 2009; 39: 299
    • 16a Asao N, Ohishi T, Sato K, Yamamoto Y. J. Am. Chem. Soc. 2001; 123: 6931
    • 16b Vintonyak VV, Maier ME. Org. Lett. 2007; 9: 655
    • 17a Labonne A, Kribber T, Hintermann L. Org. Lett. 2006; 8: 5853
    • 17b Boeck F, Kribber T, Xiao L, Hintermann L. J. Am. Chem. Soc. 2011; 133: 8138
    • 18a Lindgren BO, Nilsson T. Acta Chem. Scand. 1973; 27: 888
    • 18b Kraus GA, Roth B. J. Org. Chem. 1980; 45: 4825
    • 18c Bal BS, Childers WE. Jr, Pinnick HW. Tetrahedron 1981; 2091
    • 19a Muraoka O, Zheng B, Okumura K, Tanabe G, Momose T, Eugster CH. J. Chem. Soc., Perkin Trans. 1 1996; 1567
    • 19b Mayer C, Trueb W, Wilson J, Eugster CH. Helv. Chim. Acta 1968; 51: 661
  • 20 Behan JM, Johnstone RA. W, Wright MJ. J. Chem. Soc., Perkin. Trans. 1 1975; 1216

    • For reviews, see:
    • 21a Tzirakis MD, Lykakis IN, Orfanopoulos M. Chem. Soc. Rev. 2009; 38: 2609
    • 21b Tanielian C. Coord. Chem. Rev. 1998; 178-180: 1165
    • 21c Hill CL. Synlett 1995; 127
    • 22a Dondi D, Fagnoni M, Albini A. Chem. Eur. J. 2006; 12: 4153
    • 22b Esposti S, Dondi D, Fagnoni M, Albini A. Angew. Chem. Int. Ed. 2007; 46: 2531

      For reviews, see:
    • 23a Nicolaou KC, Ellery SP, Chen JS. Angew. Chem. Int. Ed. 2009; 48: 7140
    • 23b Edmonds DJ, Johnston D, Procter DJ. Chem. Rev. 2004; 104: 3371