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Synthesis 2010(13): 2179-2200  
DOI: 10.1055/s-0029-1220007
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Cyclopentadienylcobalt-Mediated Intermolecular Cycloaddition of α,ω-Diynes to (Cyclo)alkenes: Synthesis of Linearly Fused Oligocycles and Extension to Enantiomerically Pure (6aR,10aR)-Dihydroanthracyclinones

Corinne Auberta, Vincent Gandonb, Sangdon Hanc, Barry M. Johnsonc, Max Malacriaa, Sten Schömenauerc, K. Peter C. Vollhardt*c, Glenn D. Whitenerc
a UPMC Université Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France
b Université Paris-Sud, UMR CNRS 8182, 91405 Orsay, France
c Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, USA
Fax: +1(510)6435208; e-Mail: kpcv@berkeley.edu;
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Publication History

Received 26 March 2010
Publication Date:
18 May 2010 (online)

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Abstract

The generality of the [CpCoL2]-mediated [2+2+2] cycloaddition of α,ω-diynes to (cyclo)alkenes has been extended to include linear oligocycles as models for the one-step, A + D → ABCD construction of optically pure, novel 6,10-dihydroanthracyclinones.

Key words

alkenes - alkynes - cycloadditions - polycycles - transition metals

    References

  • For recent reviews, see:
  • 1a Galan BR. Rovis T. Angew. Chem. Int. Ed.  2009,  48:  2830 
    Search in Google Scholar
  • 1b Hess W. Treutwein J. Hilt G. Synthesis  2009,  3537 
  • 1c Ogasawara M. Watanabe S. Synthesis  2009,  1761 
  • 1d Shibata T. Tsuchikama K. Org. Biomol. Chem.  2008,  6:  1317 
    Search in Google Scholar
  • 1e Scheuermann née Taylor CJ. Ward BD. New J. Chem.  2008,  32:  1850 
    Search in Google Scholar
  • 1f Omae I. Appl. Organometal. Chem.  2008,  22:  149 
    Search in Google Scholar
  • 1g Rayabarapu DK. Cheng C.-H. Acc. Chem. Res.  2007,  40:  971 
    Search in Google Scholar
  • 1h Tanaka K. Nishida G. Sagae H. Hirano M. Synlett  2007,  1426 
  • 1i Heller B. Hapke M. Synlett  2007,  1085 
  • 1j Agenet N. Buisine O. Slowinski F. Gandon V. Aubert C. Malacria M. Org. React.  2007,  68:  1 
    Search in Google Scholar
  • For selected reviews specifically dealing with CpCo-mediated cooligomerizations of unsaturated substrates, see:
  • 1k Vollhardt KPC. Angew. Chem., Int. Ed. Engl.  1984,  23:  539 
    Search in Google Scholar
  • 1l See also: Vollhardt KPC. Lect. Heterocycl. Chem.  1987,  9:  59 
    Search in Google Scholar
  • 1m See also: Miljanić OŠ. Vollhardt KPC. In Carbon-Rich Compounds: From Molecules to Materials   Haley MM. Tykwinski RR. Wiley-VCH; Weinheim: 2006.  p.140 
  • 2a García-Rubín S. Varela JA. Castedo L. Saá C. Chem. Eur. J.  2008,  14:  9772 
    Search in Google Scholar
  • 2b Kim DH. Chung YK. Han JW. Bull. Korean Chem. Soc.  2008,  29:  1224 
    Search in Google Scholar
  • 2c Alvarez LX. Bessières B. Einhorn J. Synlett  2008,  1376 
  • 2d Shibata T. Kawachi A. Ogawa M. Kuwata Y. Tsuchikama K. Endo K. Tetrahedron  2007,  63:  12853 
    Search in Google Scholar
  • 2e Tanaka K. Nishida G. Sagae H. Hirano M. Synlett  2007,  1426 
  • 2f Varela JA. Rubín SG. González-Rodriguez C. Castedo L. Saá C. J. Am. Chem. Soc.  2006,  128:  9262 
    Search in Google Scholar
  • 2g Kezuka S. Tanaka S. Ohe T. Nakaya Y. Takeuchi R. J. Org. Chem.  2006,  71:  543 
    Search in Google Scholar
  • 2h Tsuchikama K. Kuwata Y. Shibata T. J. Am. Chem. Soc.  2006,  128:  13686 
    Search in Google Scholar
  • 2i Wu Y.-T. Hayama T. Baldridge KK. Linden A. Siegel JS. J. Am. Chem. Soc.  2006,  128:  6870 
    Search in Google Scholar
  • 2j Wu M.-S. Rayabarapu DK. Cheng C.-H. Tetrahedron  2004,  60:  10005 
    Search in Google Scholar
  • 2k Sung MJ. Pang J.-H. Park S.-B. Cha JK. Org. Lett.  2003,  5:  2137 
    Search in Google Scholar
  • 2l Nishikawa T. Shinokubo H. Oshima K. J. Am. Chem. Soc.  2001,  123:  4629 
    Search in Google Scholar
  • 2m Sambaiah T. Huang D.-J. Cheng C.-H. J. Chem. Soc., Perkin Trans. 1  2000,  195 
  • 2n Yamamoto Y. Kitahara H. Ogawa R. Kawaguchi H. Tatsumi K. Itoh K. J. Am. Chem. Soc.  2000,  122:  4310 
    Search in Google Scholar
  • 2o Son SU. Choi DS. Chung YK. Lee S.-G. Org. Lett.  2000,  2:  2097 
    Search in Google Scholar
  • 2p Ozerov OV. Patrick BO. Ladipo FT. J. Am. Chem. Soc.  2000,  122:  6423 
    Search in Google Scholar
  • 2q Sambaiah T. Li L.-P. Huang D.-J. Lin C.-H. Rayabarapu DK. Cheng C.-H. J. Org. Chem.  1999,  64:  3663 
    Search in Google Scholar
  • 2r Tsuda T. J. Mol. Catal. A  1999,  147:  11 ; and references cited therein
    Search in Google Scholar
  • 2s Hsiao T.-Y. Santhosh KC. Liou K.-F. Cheng C.-H. J. Am. Chem. Soc.  1998,  120:  12232 
    Search in Google Scholar
  • 2t Huang D.-J. Sambaiah T. Cheng C.-H. New J. Chem.  1998,  22:  1147 
    Search in Google Scholar
  • 2u Yamamoto Y. Kitahara H. Ogawa R. Itoh K. J. Org. Chem.  1998,  63:  9610 
    Search in Google Scholar
  • 2v Ikeda S. Watanabe H. Sato Y. J. Org. Chem.  1998,  63:  7026 
    Search in Google Scholar
  • 2w Yamamoto Y. Kitahara H. Hattori R. Itoh K. Organometallics  1998,  17:  1910 
    Search in Google Scholar
  • 2x Johnson ES. Balaich GJ. Rothwell IP. J. Am. Chem. Soc.  1997,  119:  7685 ; and references cited therein
    Search in Google Scholar
  • 2y Zhou Z. Costa M. Chiusoli GP. J. Chem. Soc., Perkin Trans. 1  1992,  1399 ; and references cited therein
  • 2z Grigg R. Scott R. Stevenson P. J. Chem. Soc., Perkin Trans. 1  1988,  1365 
  • 3 For recent work, see: Amslinger S. Aubert C. Gandon V. Malacria M. Paredes E. Vollhardt KPC. Synlett  2008,  2056 ; and references cited therein
    Thieme Connect
  • 4a Boryldiynes: Geny A. Lebuf D. Rouquié G. Vollhardt KPC. Malacria M. Gandon V. Aubert C. Chem. Eur. J.  2007,  13:  5408 
    Search in Google Scholar
  • 4b See also: Gandon V. Lebuf D. Amslinger S. Vollhardt KPC. Malacria M. Aubert C. Angew. Chem. Int. Ed.  2005,  44:  7114 
    Search in Google Scholar
  • 4c Pyridones: Aubert C. Betschmann P. Eichberg MJ. Gandon V. Geny A. Heckrodt TJ. Lehmann J. Malacria M. Masjost B. Paredes E. Vollhardt KPC. Whitener GD. Chem. Eur. J.  2007,  13:  7443 
    Search in Google Scholar
  • 4d Pyrimidines: Pellissier H. Rodriguez J. Vollhardt KPC. Chem. Eur. J.  1999,  5:  3549 
    Search in Google Scholar
  • 4e Indoles: Boese R. Van Sickle AP. Vollhardt KPC. Synthesis  1994,  1374 
  • 5 For a collection of recent reviews, see: Anthracycline Chemistry and Biology, Topics in Current Chemistry   Vol. 282-283:  Krohn K. Springer; Berlin: 2008. 
  • For this scheme and preliminary examples of its execution, see:
  • 6a Johnson BM. Vollhardt KPC. Synlett  1990,  209 
  • 6b Malaska M. Vollhardt KPC. In Advances in Natural Products Chemistry   . Harwood Academic Publishers; Chur: 1992.  p.53 
  • 7 For related cocyclizations of 1,2-dipropynoylarenes with alkynes to give anthraquinones, see: Tanaka K. Suda T. Noguchi K. Hirano M. J. Org. Chem.  2007,  72:  2243 ; and references cited therein
    CrossrefSearch in Google Scholar
  • 8 Kreye P, Groth U, and Eckenberg P. inventors; German Patent DE19708496  (A1). A tether version of this approach has been described in a (withdrawn) patent application: ; Chem. Abstr. 1998, 129, 230575
  • 9 Macomber DW. Verma AG. Rogers RD. Organometallics  1988,  7:  1241 
    CrossrefSearch in Google Scholar
  • 10 Aubert C. Gandon V. Heckrodt TJ. Malacria M. Paredes E. Vollhardt KPC. Chem. Eur. J.  2007,  13:  7466 
    CrossrefSearch in Google Scholar
  • 11a Gesing ERF. Vollhardt KPC. J. Organomet. Chem.  1981,  217:  105 
    Search in Google Scholar
  • 11b For a similar result with a functionalized 17, see: Eckenberg P. Groth U. Synlett  2003,  2188 
  • 12 Pearson AJ. Shively RJ. Organometallics  1994,  13:  578 
    CrossrefSearch in Google Scholar
  • 13a Clinet J.-C. Duñach E. Vollhardt KPC. J. Am. Chem. Soc.  1983,  105:  6710 
    Search in Google Scholar
  • 13b Butenschön H. Winkler M. Vollhardt KPC. J. Chem. Soc., Chem. Commun.  1986,  388 
  • 13c Grotjahn DB. Vollhardt KPC. J. Am. Chem. Soc.  1986,  108:  2091 
    Search in Google Scholar
  • 14 Winter W. Müller E. Synthesis  1974,  709 
    Thieme Connect
  • 15 Hillard RL. Vollhardt KPC. J. Am. Chem. Soc.  1977,  99:  4058 
    Search in Google Scholar
  • 16 For related literature, see, inter alia: Canonne P. Plamondon J. Akssira I. Tetrahedron  1988,  44:  2903 
    Search in Google Scholar
  • 17 See also: Arbuzov BA. Klimovitskii EN. Aganov AV. Sergeeva GN. Izv. Akad. Nauk. SSSR, Ser. Khim.  1979,  2807 ; Chem. Abstr. 1979, 92, 128501
  • 18 Johnson BM. Vollhardt KPC. Synlett  1990,  209 
    Thieme Connect
  • X-ray structures:
  • 19a

    For compound 54, an X-ray structure was determined by Professor Ling-Kang Liu of the National Taiwan University, Taiwan, in 1987, and a cif file could not be generated. For structure tables and coordinates, please contact the primary author.

  • 19b

    CCDC 770347 and CCDC 770348 contain the supplementary crystallographic data for 66 and 67, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

  • 20 Wagner J, Van Eis M, Von Matt P, Evenou J.-P, and Schuler W. inventors; PCT Int. Appl. WO 2007006533 A2  20070118.  ; Chem. Abstr. 2007, 146, 163003
  • 21 For a recent review, see: Koch TH. Barthel BL. Kalet BT. Rudnicki DL. Post GC. Burkhart DJ. Top. Curr. Chem.  2008,  283:  141 ; and references cited therein
    Search in Google Scholar
  • For some pertinent selected examples of related keto-phenol equilibria, see:
  • 22a García E. Kündig EP. Lomberget T. Bragg R. Poulard C. Bernardinelli G. Chimia  2007,  61:  169 ; and references cited therein
    Search in Google Scholar
  • 22b Mattar SM. Emwas AH. Calhoun LA. J. Phys. Chem. A  2004,  108:  11545 ; and references cited therein
    Search in Google Scholar
  • 22c Halton B. Jones CS. Kay AJ. Margetic D. Sretenovic S. J. Chem. Soc., Perkin Trans. 1  2000,  2205 
  • 22d Bulman-Page PC. Ley SV. J. Chem. Soc., Perkin Trans. 1  1984,  1847 
  • 22e Oda N. Nagai S.-I. Ito I. Chem. Pharm. Bull.  1979,  27:  2229 
    Search in Google Scholar
  • 22f Pearson MS. Jensky BJ. Greer FX. Hagstrom JP. Wells NM. J. Org. Chem.  1978,  43:  4617 
    Search in Google Scholar
  • 22g Lee WW. Martinez AP. Smith TH. Henry DW. J. Org. Chem.  1976,  41:  2296 
    Search in Google Scholar
  • 23 Dimmel DR. Shepard D. J. Org. Chem.  1982,  47:  22 
    CrossrefSearch in Google Scholar
  • 24 For an illustrative X-ray structure of a related molecule, see: Tsuda T. Morikawa S. Hasegawa N. Saegusa T. J. Org. Chem.  1990,  55:  2978 
    Search in Google Scholar
  • 25 For spectral data, see: Rodríguez D. Castedo L. Domínguez D. Saá C. Org. Lett.  2003,  5:  3119 
    CrossrefSearch in Google Scholar
  • 26 Rausch MD. Genetti RA. J. Org. Chem.  1970,  35:  3888 
    Search in Google Scholar
  • 27 Jonas K. Deffense E. Habermann D. Angew. Chem., Int. Ed. Engl.  1983,  22:  716 
    Search in Google Scholar
  • 28 Boykin DW. Dewprashad B. Eisenbraun E. J. Org. Chem.  1990,  55:  425 
    CrossrefSearch in Google Scholar
  • 29 Robertson JS. Dunstan PJ. Biochem. J.  1972,  127:  119 
    Search in Google Scholar
  • 30 Komarov NV. Yarosh OG. Zh. Obshch. Khim.  1967,  37:  264 ; Chem. Abstr. 1967, 66, 95126
    Search in Google Scholar
  • 31 Fieser LF. Fieser M. Reagents for Organic Synthesis   Vol. 1:  Wiley; New York: 1967.  p.142 
    Search in Google Scholar