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Volumn 102, Issue 16, 1980, Pages 5253-5261

Transition-Metal-Catalyzed Alkyne Cyclizations. A Cobalt-Mediated Total Synthesis of dl-Estrone

Author keywords

[No Author keywords available]

Indexed keywords

ESTROGEN; ESTRONE;

EID: 0019125839     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00536a023     Document Type: Article
Times cited : (174)

References (51)
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    • Taken in part from the Ph.D. Thesis of R. L. Funk, University of California, Berkeley
    • Taken in part from the Ph.D. Thesis of R. L. Funk, University of California, Berkeley, 1978.
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  • 3
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    • 1976-1980; Camille and Henry Dreyfus Teacher-Scholar, 1978-.
    • Fellow of the Alfred P. Sloan Foundation, 1976-1980; Camille and Henry Dreyfus Teacher-Scholar, 1978-1983.
    • (1983) Fellow of the Alfred P. Sloan Foundation
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    • Total Steroid Synthesis
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    • Preliminary reports of this work have appeared: 99, 5483 (1977); 101, 215 (1979). The conceptual scheme of a steroid synthesis via cobalt catalysis was conceived by us in 1973 and first publicly outlined at the 30th Annual Northwest Regional Meeting of the American Chemical Society, Honolulu, Hawaii, June
    • Preliminary reports of this work have appeared: R. L. Funk and K. P. C. Vollhardt, J. Am. Chem. Soc., 99, 5483 (1977); 101, 215 (1979). The conceptual scheme of a steroid synthesis via cobalt catalysis was conceived by us in 1973 and first publicly outlined at the 30th Annual Northwest Regional Meeting of the American Chemical Society, Honolulu, Hawaii, June 12-13, 1975.
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    • in press; W. Oppolzer, Synthesis, 793 (1978); T. Kametani, Pure Appl. Chem.
    • For recent reviews, see R. L. Funk and K. P. C. Vollhardt, Chem. Soc. Rev., in press; W. Oppolzer, Synthesis, 793 (1978); T. Kametani, Pure Appl. Chem., 51, 747 (1979).
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    • 4433 (1977); L. S. Meriwether, E. C. Colthup, G. W. Kennerly, and R. N. Reusch, J. Org. Chem., 26, 5155 (1961); E. Milller, Synthesis
    • M. A. Pericas and F. Serratosa, Tetrahedron Lett., 4433 (1977); L. S. Meriwether, E. C. Colthup, G. W. Kennerly, and R. N. Reusch, J. Org. Chem., 26, 5155 (1961); E. Milller, Synthesis, 761 (1974).
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    • For a mechanistic discussion, 10, 1 (1977); R. L. Hillard III and K. P. C. Vollhardt, J. Am. Chem. Soc.
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    • Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry
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    • Each pair of diastereomers showed only one methyl singlet absorption in the ‘H NMR spectrum with the methyl protons of the diastereomers 29 shielded relative to the methyl protons in 30. Curiously, all of the carbon-13 resonances but one were isochronous for the diastereomers 29, whereas all but five carbons for the diastereomers 30 were isochronous. Again, the methyl carbons of 29 (15.74 ppm) were sterically shielded relative to the methyl carbons of 30 (19.81, 19,47 ppm).
    • Gratifyingly, upon chromatographic purification the diastereomers 29 could be readily and completely separated from the unwanted diastereomers 30. Each pair of diastereomers showed only one methyl singlet absorption in the ‘H NMR spectrum with the methyl protons of the diastereomers 29 shielded relative to the methyl protons in 30. Curiously, all of the carbon-13 resonances but one were isochronous for the diastereomers 29, whereas all but five carbons for the diastereomers 30 were isochronous. Again, the methyl carbons of 29 (15.74 ppm) were sterically shielded relative to the methyl carbons of 30 (19.81, 19,47 ppm).
    • Gratifyingly, upon chromatographic purification the diastereomers 29 could be readily and completely separated from the unwanted diastereomers 30.
  • 44
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    • On the other hand, 2-acetylestra-l,3,5(10)-trien-17-one can be selectively oxidized to the 2-acetoxyestratrienone
    • On the other hand, 2-acetylestra-l,3,5(10)-trien-17-one can be selectively oxidized to the 2-acetoxyestratrienone: T. Nambara, S. Honma, and S. Akiyama, Chem. Pharm. Bull., 18, 474 (1970).
    • (1970) Chem. Pharm. Bull. , vol.18 , pp. 474
    • Nambara, T.1    Honma, S.2    Akiyama, S.3


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