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14
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33947450396
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The possibility of epimerizing a cis junction, obtained from a Diels-Alder reaction, to the trans series was well recognized and practiced by Woodward and co-workers in their total synthesis of steroids. Other instances of epimerization are also cited herein. (a)
-
The possibility of epimerizing a cis junction, obtained from a Diels-Alder reaction, to the trans series was well recognized and practiced by Woodward and co-workers in their total synthesis of steroids. Other instances of epimerization are also cited herein. (a) Woodward, R. B.; Sondheimer, F.; Taub, D.; Heusler, K.; McLamore, W. M. J. Am. Chem. Soc. 1952, 74, 4223-4251.
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15
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16
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Of course, this approach requires a vicinal keto group to enable epimerization and the capacity to apply strict thermodynamic or kinetic controls to govern the junction stereochemistry
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(c) Mukhopadhyay, A.; Ali, S. M.; Husain, M.; Suryawanshi, S. N.; Bhakuni, D. S. Tetrahedron Lett. 1989, 30, 1853-1856. Of course, this approach requires a vicinal keto group to enable epimerization and the capacity to apply strict thermodynamic or kinetic controls to govern the junction stereochemistry.
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Following completion of this work, we noted that in footnote 18 in ref 10, Professor Corey futuristically envisioned potential value of reductive denitration at the junction. However no results are provided. Nonetheless the kernel of the idea can be found in Corey's comment.
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Cycloaddition of compound 3 with several 2-silyloxy-1,3-butadienes as well as diene 8 in toluene under the variety of conditions did not proceed at all.
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