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(a) For a review of early pioneering partial syntheses see ref 2.
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(a) A total synthesis of digitoxigenin, which represents the first total synthesis of a cardenolide from nonsteroid starting materials, has recently been accomplished: Stork, G.; West, F.; Lee, H. Y.; Isaacs, R. C. A.; Manabe, S. J. Am. Chem. Soc. 1996, 118, in press.
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(b) For total synthesis approaches from nonsteroid starting materials, see: Daniewski, A. R.; Valenta, Z.; White, P. S. Bull. Pol. Acad. Sci., Chem. 1984, 32, 29. Stork, G.; Mook, R. J. Am. Chem. Soc. 1983, 105, 3720. Daniewski, A. R.; Kabat, M. M.; Masnyk, M.; Wicha, J.; Wojciechowska, W. J. Org. Chem. 1988, 53, 4855. Ruel, R.; Deslongchamps, P. Can. J. Chem. 1992, 70, 1939. Rawal, V. H.; Iwasa, S. Abstracts of Papers; 204th National Meeting of the American Chemical Society, Washington, DC; American Chemical Society: Washington, 1992; ORGN 35.
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19
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(b) Mathre, D. J.; Thompson, A. S.; Douglas, A. W.; Hoogsteen, K.; Carroll, J. D.; Corley, E. G.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 2880.
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21
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84889522785
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note
-
13C NMR, IR, and MS analysis, while elemental composition was confirmed by combustion analysis or high-resolution mass spectrometry.
-
-
-
-
22
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84889550866
-
-
note
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Determined by GLC analysis on a Cyclodex B capillary column.
-
-
-
-
23
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84889505592
-
-
note
-
The ee of 5 was 96-98% when 0.5 equiv of oxazaborolidine 4 was employed.
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-
-
-
24
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0002939651
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(a) Ireland, R. E.; Thaisrivongs, S.; Vanier, N.; Wilcox, C. S. J. Org. Chem. 1980, 45, 48.
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0001997183
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(b) For a recent review of the Ireland-Claisen rearrangement, see: Pereira, S.; Srebnik, M. Aldrichim. Acta 1993, 26, 17.
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(b) Hajos, Z. G.; Parrish, D. R.; Oliveto, E. P. Tetrahedron 1968, 24, 2039.
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34
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84889502288
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note
-
Crystallographic data for this intermediate have been deposited with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
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