Tandem Diels-Alder/Double Intramolecular Two-Alkyne Annulations of Fischer Carbene Complexes: A One-Pot Construction of All Four Rings of the Steroid Ring System

Journal of the American Chemical Society

Volumn 113, Issue 26, 1991, Pages 9873-9875

  Bao, Jianming ^a   Dragisich, Vera ^a   Wenglowsky, Steve ^a   Wulff, William D ^a  

^a UNIVERSITY OF CHICAGO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001313853     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00026a036     Document Type: Article

References (37)

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3. Wulff, W. D. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press Inc.: Greenwich, CT, 1989; Vol. 1.
4. Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 5.
5. For a list of citations to syntheses, see ref Id and footnote 6 in the following: Wulff, W. D.; Bauta, W. E.; Kaesler, R. W.; Lankford, P. J.; Miller, R. A.; Murray, C. K.; Yang, D. C. J. Am. Chem. Soc. 1990, 112, 3642.
6. For recent syntheses not cited in references Id or 2, see: Yamashita, A.; Toy, A.; Scahill, T. A. J. Org. Chem. 1989, 54, 3625.
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25. This work was presented in preliminary form at the 201st National Meeting of the American Chemical Society, Atlanta, GA, April 14–19, 1991; Abstract 196.
26. The chromium complex 6c was prepared in 51% yield by alkylation of (metnylmethoxymethylene)pentacarbonylchromium(O) with 1-undeca-4,9-diynyl triflate according to procedures for related complexes Complexes 6a and 6b were prepared in a related manner in 72 and 38% yields, respectively. The tungsten complex 7a was prepared in 57% yield by the standard Fischer procedure1 from tungsten hexacarbonyl and l-lithioundeca-4,9-diyne, which in turn was generated from the corresponding iodide.10 The complexes 7b and 7c were prepared in a similar manner in 44 and 28% yield, respectively.
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33. Upon completion of the Diels-Alder reaction (16 h), the solution was diluted 10-fold with acetonitrile, then sealed in a reaction flask with a threaded stopcock14 at 25 °C under 1 atm of CO, and heated to 110 °C for 23 h.
34. Chan, K. S.; Peterson, G. A.; Brandvold, T. A.; Faron, K. L.; Challener, C. A.; Hyldahl, C.; Wulff, W. D. J. Organomet. Chem. 1987, 334, 9.
35. 1,5-Hexadiyne was deprotonated with 1.0 equiv of n-butyllithium in THF at −78 °C, then treated with 1.0 equiv of triflate S, and upon warming to 0 °C gave a 55% yield of triyne 4a. The triyne 4a was converted to complexes 3a and 3b in 66 and 52% yields, respectively, according to procedures for related alkynyl carbene complexes.
36. Chan, K. S.; Wulff, W. D. J. Org. Chem. 1986, 108, 5239.
37. Lecker, S. H.; Nguyen, N. H.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1986, 108, 856.