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Volumn 62, Issue 18, 1997, Pages 6344-6352

A Short, Efficient Copper-Mediated Synthesis of 1α,25-Dihydroxyvitamin D2 (1α,25-Dihydroxyergocalciferol) and C-24 Analogs

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EID: 0000631889     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970604u     Document Type: Article
Times cited : (30)

References (95)
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    • This paper is dedicated to Professor Dieter Seebach in honor of his 60th birthday
    • This paper is dedicated to Professor Dieter Seebach in honor of his 60th birthday.
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    • This work was taken in part from the doctoral thesis of Mercedes Torneiro University of Santiago de Compostela, January 1994
    • This work was taken in part from the doctoral thesis of Mercedes Torneiro (University of Santiago de Compostela, January 1994).
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    • Although the overall yield of the Julia olefination method is genearally lower than that of the Wittig approach, high yields have been obtained in some cases. For examples of the Julia olefination, see; (a) Yamada, S.; Shiraishi, M.; Ohmori, M.; Takayama, H. Tetrahedron Lett. 1984, 25, 3347. (b) Wicha, J.; Bal, K.; Piekut, S. Synth. Commun. 1977, 7, 215. (c) Perlman, K. L.; Sicinski, R. R.; Phelps, M. E.; Schnoes, H. K.; DeLuca, H. F. Tetrahedron Lett. 1987, 28, 6129. (d) Sicinski, R. R.; DeLuca, H. F.; Schnoes, H. K.; Tanaka, Y.; Smith, C. M. Bioorg. Chem. 1987, 15, 15. (e) Perlman, K. L.; DeLuca, H. F. Tetrahedron Lett. 1992, 33, 2937. (f) Kutner, A.; Chodynski, M.; Halkes, S. J.; Brugman. J. Bioorg. Chem. 1993, 21, 13.
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    • Although the overall yield of the Julia olefination method is genearally lower than that of the Wittig approach, high yields have been obtained in some cases. For examples of the Julia olefination, see; (a) Yamada, S.; Shiraishi, M.; Ohmori, M.; Takayama, H. Tetrahedron Lett. 1984, 25, 3347. (b) Wicha, J.; Bal, K.; Piekut, S. Synth. Commun. 1977, 7, 215. (c) Perlman, K. L.; Sicinski, R. R.; Phelps, M. E.; Schnoes, H. K.; DeLuca, H. F. Tetrahedron Lett. 1987, 28, 6129. (d) Sicinski, R. R.; DeLuca, H. F.; Schnoes, H. K.; Tanaka, Y.; Smith, C. M. Bioorg. Chem. 1987, 15, 15. (e) Perlman, K. L.; DeLuca, H. F. Tetrahedron Lett. 1992, 33, 2937. (f) Kutner, A.; Chodynski, M.; Halkes, S. J.; Brugman. J. Bioorg. Chem. 1993, 21, 13.
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    • and references therein
    • For examples of subsitution reactions at an allylic carbon, see: (a) Yanagisawa, A.; Noritake, Y.; Nomura, N.; Yamamoto, H. Synlett 1991, 251 and references therein, (b) Yanagisawa, A.; Nomura, N.; Yamamoto, H. Synlett 1993, 689. (c) Flemming, S.; Kabbara, J.; Nickisch, K.; Westermann, J.; Mohr, J. Synlett 1995, 183. (d) Persson, S. M., Klaveen, M. v.; Grove, D. M.; Bäckvall, J. E.; Koten, G. v. Chem. Eur. J. 1995 J. 351 and references therein.
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    • For examples of subsitution reactions at an allylic carbon, see: (a) Yanagisawa, A.; Noritake, Y.; Nomura, N.; Yamamoto, H. Synlett 1991, 251 and references therein, (b) Yanagisawa, A.; Nomura, N.; Yamamoto, H. Synlett 1993, 689. (c) Flemming, S.; Kabbara, J.; Nickisch, K.; Westermann, J.; Mohr, J. Synlett 1995, 183. (d) Persson, S. M., Klaveen, M. v.; Grove, D. M.; Bäckvall, J. E.; Koten, G. v. Chem. Eur. J. 1995 J. 351 and references therein.
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    • For examples of subsitution reactions at an allylic carbon, see: (a) Yanagisawa, A.; Noritake, Y.; Nomura, N.; Yamamoto, H. Synlett 1991, 251 and references therein, (b) Yanagisawa, A.; Nomura, N.; Yamamoto, H. Synlett 1993, 689. (c) Flemming, S.; Kabbara, J.; Nickisch, K.; Westermann, J.; Mohr, J. Synlett 1995, 183. (d) Persson, S. M., Klaveen, M. v.; Grove, D. M.; Bäckvall, J. E.; Koten, G. v. Chem. Eur. J. 1995 J. 351 and references therein.
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    • and references therein
    • For examples of subsitution reactions at an allylic carbon, see: (a) Yanagisawa, A.; Noritake, Y.; Nomura, N.; Yamamoto, H. Synlett 1991, 251 and references therein, (b) Yanagisawa, A.; Nomura, N.; Yamamoto, H. Synlett 1993, 689. (c) Flemming, S.; Kabbara, J.; Nickisch, K.; Westermann, J.; Mohr, J. Synlett 1995, 183. (d) Persson, S. M., Klaveen, M. v.; Grove, D. M.; Bäckvall, J. E.; Koten, G. v. Chem. Eur. J. 1995, 1. 351 and references therein.
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    • It is known that simple vinyl carbanions react with steroidal 22-aldehydes with poor stereoselectivity to give the Cram (R)-allylic alcohol as the major product. For a few examples, see: ref 20, and (a) Khripach, V. A.; Zhabinskiy, V. N.; Olkhovick, V. K. Tetrahedron Lett. 1990, 31, 4937. (b) Back, T. G.; Blazecka, P. G.; Krishna, M. V. Tetrahedron Lett. 1991, 32, 4817.
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    • It is known that simple vinyl carbanions react with steroidal 22-aldehydes with poor stereoselectivity to give the Cram (R)-allylic alcohol as the major product. For a few examples, see: ref 20, and (a) Khripach, V. A.; Zhabinskiy, V. N.; Olkhovick, V. K. Tetrahedron Lett. 1990, 31, 4937. (b) Back, T. G.; Blazecka, P. G.; Krishna, M. V. Tetrahedron Lett. 1991, 32, 4817.
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    • While this work was in progress, a catalytic version of the Yamamoto reaction appeared. See ref 30b
    • While this work was in progress, a catalytic version of the Yamamoto reaction appeared. See ref 30b.
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    • note
    • 2 regioisomers and other stereoisomers with Z configuration at the double bond were chromatographically removed after desilylation.
  • 84
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    • note
    • 3 hormone receptor.
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    • 2O have not been carried out
    • 2O have not been carried out.
  • 91
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    • note
    • Previous experiments carried out in our laboratory indicate that the Wittig-Horner type coupling gives the vitamin D triene unit in low yield when the amount of CD-side chain fragment used is lower than 50 mg.
  • 92
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    • Attempts to carry out this type of transformation using other cuprates have not been pursued although similar results are expected
    • Attempts to carry out this type of transformation using other cuprates have not been pursued although similar results are expected.


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