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Synthesis 2008(15): 2323-2326  
DOI: 10.1055/s-2008-1067175
SHORTPAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Concise Enantioselective Strategy to (+)-(R)-Goniothalamin and (+)-(R)-Goniothalamin Oxide by Employing Hydrolytic Kinetic Resolution and Ring-Closing Metathesis as Key Steps

D. Subhas Bose*, A. V. Narsimha Reddy, Bingi Srikanth
Organic Chemistry Division III, Fine Chemicals Laboratory, Indian Institute of Chemical Technology, Hyderabad 500007, India
Fax: +91(40)27160387; e-Mail: dsb@iict.res.in; e-Mail: bose_iict@yahoo.co.in;
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Publication History

Received 10 April 2008
Publication Date:
08 July 2008 (online)

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Abstract

An efficient and general strategy to (R)-goniothalamin and (R)-goniothalamin oxide is described by using Jacobsen’s hydrolytic­ kinetic resolution of racemic epoxide and ring-closing metathesis (RCM) as key steps, which provided a rapid access to these natural products that display a fascinating array of biological activity. (R)-Goniothalamin oxide was prepared in high yield and diastereomeric excess under various epoxidation conditions.

Key words

Jacobsen’s epoxidation - goniothalamin - styryl lactones - metathesis - natural products

    References

  • 1a Vara Prasad JVN. Para KS. Lunney EA. Ortwine DF. Dunbar JB. Ferguson D. Tummino PJ. Hupe D. Tait BD. Domagala JM. Humblet C. Bhat TN. Liu B. Guerin DAM. Baldwin ET. Erickson JW. Sawyer TK. J. Am. Chem. Soc.  1994,  116:  6989 
    Google Scholar
  • 1b Evidente A. Cabras A. Maddau L. Serra S. Andolfi A. Motta A. J. Agric. Food Chem.  2003,  51:  6957 
    Google Scholar
  • 1c Segre AL. Logrieco A. Nature Toxins  1999,  7:  133 
    Google Scholar
  • 1d Shi X. Leal WS. Liu Z. Schrader E. Meinwald J. Tetrahedron Lett.  1995,  36:  71 
    Google Scholar
  • 2a Harris JM. Keranen MD. Nguyen H. Young VG. O’Doherty GA. Carbohydr. Res.  2000,  328:  17 
    Google Scholar
  • 2b Nicolaou KC. Mitchell HJ. Angew. Chem. Int. Ed.  2001,  40:  1577 
    Google Scholar
  • 3a Ali A. Mackeen MM. Hamid M. Aun QB. Zauyah Y. Azimahtol HLP. Kawazu K. Planta Med.  1997,  63:  81 
    Google Scholar
  • 3b Cao SG. Wu XH. Sim KY. Tan BKH. Pereira JT. Goh SH. Tetrahedron  1998,  54:  2143 
    Google Scholar
  • 3c Lan YH. Chang FR. Yu JH. Yang YL. Chang YL. Lee SJ. Wu YC. J. Nat. Prod.  2003,  66:  487 
    Google Scholar
  • 4 Hlubucek JR. Robertson AV. Aust. J. Chem.  1967,  20:  2199 
    CrossrefGoogle Scholar
  • 5 Meyer HH. Liebigs Ann. Chem.  1979,  484 
    CrossrefGoogle Scholar
  • 6 Cavalheiro AJ. Yoshida M. Phytochemistry  2000,  53:  811 
    CrossrefPubMedGoogle Scholar
  • 7 Kabir KE. Khan AR. Mosaddik MA. J. Appl. Entomol.  2003,  127:  112 
    CrossrefGoogle Scholar
  • Goniothalamin was also isolated from:
  • 8a Goniothalamus giganteus: El-Zayat AE. Ferrigni NR. McCloud TG. Mckenzie AT. Byrn SR. Cassady JM. Chang C. McLuglin JL. Tetrahedron Lett.  1985,  26:  955 
    Google Scholar
  • 8b Goniothalamus uvaroids: Ahmad FB. Tukol WA. Omar S. Sharif AM. Phytochemistry  1991,  30:  2430 
    Google Scholar
  • 8c Goniothalamus malayanus, G. andersonni, G. macrophyllus, and G. velutinus: Jewers K. Blunden G. Wetchapinan S. Dougan J. Manchada AH. Davis JB. Kyi A. Phytochemistry  1972,  11:  2025 
    Google Scholar
  • 8d Goniothalamus dolichocarpus: Goh SH. Ee GCL. Chuah CH. Wei C. Aust. J. Chem.  1995,  48:  199 
    Google Scholar
  • Some of the species are widely used as traditional medicines. See:
  • 9a Kan WS. Pharmaceutical Botany   National Research Institute of Chinese Medicine; Taipei: 1979.  p.247 
    Google Scholar
  • 9b Surivet JP. Vatele J.-M. Tetrahedron  1999,  55:  13011 
    Google Scholar
  • 10 Mosaddik MA. Haque ME. Phytother. Res.  2003,  17:  1155 
    CrossrefPubMedGoogle Scholar
  • 11 Fatima A. Kohn LK. Carvalho J. Pilli RA. Bioorg. Med. Chem.  2006,  14:  622 
    CrossrefPubMedGoogle Scholar
  • 12a Inayat-Hussain SH. Osman AB. Din LB. Ali AM. Snowden RT. MacFarlane M. Cain K. FEBS Lett.  1999,  456:  379 
    Google Scholar
  • 12b Chien ALT. Pihie AHL. J. Biochem. Mol. Biol.  2003,  36:  269 
    Google Scholar
  • 12c de Fátima A. Kohn LK. Antonio MA. de Carvalho JE. Pilli RA. Bioorg. Med. Chem.  2005,  13:  2927 
    Google Scholar
  • 13a Inayat-Hussain SH. Annuar BO. Din LB. Ali AM. Ross D. Toxicol. in Vitro  2003,  17:  433 
    Google Scholar
  • 13b Hengartner MO. Nature (London)  2000,  12:  770 
    Google Scholar
  • 13c Srinivasula SM. Ahmad M. Fernandes-Alnemri T. Alnemri ES. Mol. Cell  1998,  1:  949 
    Google Scholar
  • 13d Yang J. Liu X. Bhalla K. Kim CN. Ibrado AM. Cai J. Peng TI. Jones DP. Wang X. Science  1997,  275:  1129 
    Google Scholar
  • 14 Chem WY. Wu CC. Lan YH. Chang FR. Teng CM. Wu WC. Eur. J. Pharm.  2005,  522:  20 
    CrossrefPubMedGoogle Scholar
  • 15 de Fátima A. Marquissolo C. de Albuquerque S. Carraro-Abrahão AA. Pilli RA. Eur. J. Med. Chem.  2006,  41:  1210 
    CrossrefGoogle Scholar
  • Selected examples:
  • 16a O’Connor B. Just G. Tetrahedron Lett.  1986,  27:  5201 
    Google Scholar
  • 16b Bennet F. Knight DW. Tetrahedron Lett.  1988,  29:  4625 
    Google Scholar
  • 16c Bennett F. Knight DW. Fenton G. J. Chem. Soc., Perkin Trans. 1  1991,  519 
    Google Scholar
  • 16d Rahman SS. Wakefield BJ. Roberts SM. Dowle MD. J. Chem. Soc., Chem. Commun.  1989,  303 
    Google Scholar
  • 16e Honda T. Kametani T. Kanai K. Tatsuzaki Y. Tsubuki M. J. Chem. Soc., Perkin Trans. 1  1990,  1733 
    Google Scholar
  • 16f Takano S. Tamikubo T. Sugihara T. Ogasawara K. Tetrahedron: Asymmetry  1992,  3:  853 
    Google Scholar
  • 16g Fuganti C. Perdrochi-Fantoni G. Sarra A. Servi S. Tetrahedron: Asymmetry  1994,  5:  1135 
    Google Scholar
  • 16h Ramachandran PV. Reddy MVR. Brown HC. Tetrahedron Lett.  2000,  41:  583 
    Google Scholar
  • 16i Job A. Wolberg M. Müller M. Enders D. Synlett  2001,  1796 
    Google Scholar
  • 16j Sundby E. Perk L. Anthonsen T. Aasen AJ. Hansen TV. Tetrahedron  2004,  60:  521 
    Google Scholar
  • 16k de Fátima A. Pilli RA. Tetrahedron Lett.  2003,  44:  8721 
    Google Scholar
  • 16l Sabitha G. Sudhakar K. Yadav JS. Tetrahedron Lett.  2006,  47:  8599 
    Google Scholar
  • 17a Tokunaga M. Larrow JF. Kakiuchi F. Jacobsen EN. Science  1997,  277:  936 
    Google Scholar
  • 17b Bose DS. Fatima L. Rajender S. Synthesis  2006,  1863 
    Google Scholar
  • For an excellent recent review, see:
  • 18a Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
    Google Scholar
  • 18b Prunet J. Angew. Chem. Int. Ed.  2003,  42:  2826 
    Google Scholar
  • 19 Merz A. Mark G. Angew. Chem., Int. Ed. Engl.  1973,  12:  845 
    CrossrefGoogle Scholar
  • 20 Braid CP. Taylor PC. J. Chem. Soc., Perkin Trans. 1  1998,  3399 
    CrossrefGoogle Scholar
  • 21 Kang SH. Kim CM. Youn JH. Tetrahedron Lett.  1999,  40:  3581 
    CrossrefGoogle Scholar
  • 22a Mitsunobu O. Synthesis  1981,  1 
    Google Scholar
  • 22b Hughes DL. Org. React.  1992,  42:  335 
    Google Scholar
  • 23 Riediker M. Duthaler RO. Angew. Chem., Int. Ed. Engl.  1989,  28:  494 
    CrossrefGoogle Scholar
  • 25a Lan Y.-H. Chang F.-R. Yu J.-H. Yang Y.-L. Chang Y.-L. Lee S.-J. Wu Y.-C. J. Nat. Prod.  2003,  66:  487 
    Google Scholar
  • 25b Sam TW. Sew-Yeu C. Matsjeh S. Gan EK. Razak D. Mohamed AL. Tetrahedron Lett.  1987,  28:  2541 
    Google Scholar
  • 26Work on a similar line has been reported:
  • 26 Pospisil J. Marko IE. Tetrahedron Lett.  2006,  47:  5933 
    CrossrefGoogle Scholar
  • 27 Lim J. Kim I.-H. Kim HH. Ahn K.-S. Han H. Tetrahedron Lett.  2001,  42:  4001 
    CrossrefGoogle Scholar
24

(+)-(R)-Goniothalamin (1): White crystalline solid; mp 82-83 ˚C (Lit. [¹6l] 81-82 ˚C). [α]D +169.4 (c 1.45, CHCl3) [Lit. [6] [α]D +170.3 (c 1.38, CHCl3)]. IR (KBr): 3050, 3025, 2931, 1722, 1610, 1245, 810, 700 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 2.55 (m, 2 H), 5.12 (dq, J 5,6 = 6.5 Hz, J 5,4 = 1.2 Hz, 1 H), 6.11 (dt, J 2,3 = 9.7 Hz, J 2,4 = 1.7 Hz, 1 H), 6.29 (dd, J 6,7 = 16.1 Hz, J 6,5 = 6.5 Hz, 1 H), 6.74 (d, J 7,6 = 15.6 Hz, 1 H), 6.94 (dt, J 3,2 = 9.7 Hz, J 3,4 = 4.4 Hz, 1 H), 7.30-7.42 (m, 5 H). ¹³C NMR (75 MHz, CDCl3): δ = 30.1, 77.9, 121.8, 125.5, 126.7, 128.4, 133.3, 135.2, 144.8, 164.1. MS (APCI): m/z (%): 201.0 (39) [M+ + H], 183.1 (100), 155.2 (66), 130.1 (41).

28

(+)-(R)-Goniothalamin Oxide (2): Mp 90-92 ˚C (Lit. [²5b] 90-94 ˚C). [α]D +100.1 (c 0.88, CHCl3) [Lit.²5b [α]D +100.7 (c 0.70, CHCl3)]. IR (KBr): 3055, 3025, 2928, 1720, 1605, 1245, 1035, 808 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 2.59 (m, 2 H), 3.28 (dd, J 6,5 = 5.6 Hz, J 6,7 = 2.0 Hz, 1 H), 3.91 (d, J 7,6 = 1.8 Hz, 1 H), 4.45 (dt, J 5,4 = 9.4 Hz, J 5,4 ¢ and 6 = 5.5 Hz, 1 H), 6.07 (dt, J 2,3 = 9.7 Hz, J 2,4 = 2.0 Hz, 1 H), 6.95 (m, 1 H), 7.32-7.39 (m, 5 H). ¹³C NMR (75 MHz, CDCl3): δ = 26.3, 57.5, 61.9, 77.2, 121.6, 125.5, 128.7, 135.5, 144.4, 164.0. MS (APCI): m/z (%) = 217.0 (100) [M+ + H], 199.0 (45), 171.1 (83), 143.1 (45), 139.0 (32), 105. 0 (31), 91.0 (31). HRMS: m/z [M + Na+] calcd for C13H12NaO3: 239.0684; found: 239.0682.