Summary
Our first target on the way towards the synthesis of nodusmicin is the preparation of the title compound. Meso diol1 is partially etherified, then oxidized to the enone. The sterically compressed structure of this compound is the rationale of the highly stereoselective introduction of the substituents. (CH3)2CuLi introduces the methyl group and the enolate is captured as silylenol ether, which in turn is transformed to the α-hydroxyketone by OsO4. Reduction leads to the vicinaltrans diol. Protection of theexo-hydroxy group is followed by treatment with sodium in ethanol. Via intramolecular nucleophilic addition, substitution and dechlorination the tetracyclic diketal8 is formed. After exchange of the protective groups and partial hydrolysis of the ketals the tertiary alkohol is obtained with methyl Grignard reagent. Acidic fragmentation yields the desired title compound.
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Literatur
Whalley H. A., Chidester C. G., Miszak S. A., Wnuk R. J. (1980) Tetrahedron Lett.: 3659
Celmer W. D., Chmurny G. N., Moppett C. E., Ware R. S., Watts P. C., Whipple E. B. (1980) J. Am. Chem. Soc.102: 4203. Weitere Antibiotika dieser Strukturgruppe: Whalley H. A., Coats J. H. (1981) 21st Interscience Conf. Antimicrob. Agents Chemother. Nr. 187; Rinehart Jr. K. L. (1984) J. Am. Chem. Soc.106: 787; Tone J., Shibakawa R., Maeda H., Yamauchi Y., Niki K., Saito M., Tsukuda K., Whipple E. B., Watts P. C., Moppett C. E., Jefferson M. T., Huang L. H., Cullen W. P., Celmer W. D. (1980) 20th Interscience Conf. Antimicrob. Agents Chemother. Nr. 62
Magerlein B. J., Reid R. J. (1982) J. Antibiot.35: 254
In jüngerer Zeit gefundene strukturell verwandte Antibiotica: Coloradocin(bis macrolid)=Luminamicin: Jackson M., Karwowski J. P., Theriault R. J., Fernandes P. B., Semon R. C., Kohl W. H. (1987) J. Antibiot.40: 1375; Rasmussen R. R., Scherr M. H., Whittern D. N., Buko A. M., McAlpine J. B. (1987) J. Antibiot.40: 1383; Omura S., Iwata R., Iwai Y., Taga S., Tanaka Y., Tomada H. (1986) J. Antibiot.39: 1323; Lustromycin: Tomada H., Iwata R., Takahashi Y., Iwai Y., Oiwa R., Omura S. (1985) J. Antibiot.38: 1205
Celmer W. D., Chmurny G. N., Moppett C. E., Ware R. S., Watts P. C., Whipple E. B. (1980) J. Am. Chem. Soc.102: 4203; Magerlein B. J., Miszak S. A. (1982) J. Antibiot.35: 111; Magerlein B. J. (1981) 182nd Nat. Meeting of the Am. Chem. Soc. Nr. Medi 72
Cane D. E., Yang, C.-C. (1984) J. Am. Chem. Soc.106: 784, 4203; (1985) J. Antibiot.38: 423; Snyder W. C., Rinehart Jr. K. L. (1984) J. Am. Chem. Soc.106: 787; Cane D. E., Ott W. R. (1988) J. Am. Chem. Soc.110: 4840
Jones R. C. F., Tunnicliffe J. H. (1985) Tetrahedron Lett.: 5845
Roush W. R., Coe J. W. (1987) Tetrahedron Lett.: 931;
Coe J. W., Roush W. R. (1989) J. Org. Chem.54: 915
Kallmerten J. (1984) Tetrahedron Lett.:25: 2843;
Plata D. J., Kallmerten J. (1987) Heterocycles25: 145;
Plata D. J., Kallmerten J. (1988) J. Am. Chem. Soc.110: 4041;
Rossano L. T., Plata D. J., Kallmerten J. (1988) J. Org. Chem.53: 5189;
Syntheseversuch von Coloradocin: Evans J. M., Kallmerten J. (1992) Synlett: 269
Gössinger E., Müller R. (1989) Tetrahedron45: 1377;
Böhm K., Gössinger E., Müller R. (1989) Tetrahedron45: 1391;
Gössinger E., Müller R., Pitterna T. (1990) Tetrahedron46: 407
Marchand A. P., LaRoe W. D., Sharma G. V. M., Suri S. C., Reddy D. S. (1986) J. Org. Chem.51: 1622
Corey E. J., Venkatesvarlu A. (1972) J. Am. Chem. Soc.94: 6190
Zimmermann K. (1991) Diplomarbeit, Wien;
Zimmermann K. (in Druck) Monatsh. Chem.
Rabideau P. W. (1989) The Conformation Analysis of Cyclohexenes, Cyclohexadienes and Related Hydroaromatic Compounds. Verlag Chemie, Weinheim
Hibbert F., Emsley J. (1990) Adv. Phys. Org. Chem.26: 255
Vgl. McDougal P. G., Rico J. G., Oh Y.-I., Condon B. D. (1986) J. Org. Chem.51: 3388. Die Autoren führen in ihren Beispielen die selektive Bildung des Monosilylethers aus symmetrischen Diolen auf die Bildung eines voluminösen Niederschlags der Base mit dem Monoanion zurück. In unserem Fall war keine Niederschlagsbildung zu beobachten
Aichberger W.-D. (1990) Diplomarbeit, Wien;
Suri S. C. (1990) Tetrahedron Lett.: 3695;
Aichberger W.-D., Gössinger E., Kratky C., Zimmermann K. (in Vorbereitung)
Bowden K., Heilbron I. M., Jones E. R. H., Weedon B. C. L. (1946) J. Chem. Soc.: 39
Dickson Jr. J. K., Tsang R., Llera J. M., Fraser-Reid B. (1989) J. Org. Chem.54: 5351
McCormick J. P., Tomasik W., Johnson M. W. (1981) Tetrahedron Lett.: 607; Sivik M. R., Gallucci J. C., Paquette L. A. (1990) J. Org. Chem.55: 391 und die dort zitierte Literatur
Hoch P. E., Stratton G. B., Colson J. G. (1969) J. Org. Chem.34: 1219
Lap B. V., Paddon-Row M. N. (1979) J. Org. Chem.44: 4979
Czernecki S., Georgoulis C., Provelenghiou C. (1976) Tetrahedron Lett.: 3535
Winstein S., Smith S., Darwish D. (1959) J. Am. Chem. Soc.81: 5511; Herter R., Föhlisch B. (1982) Synthesis: 976; Braun R., Sauer J. (1986) Chem. Ber.119: 1269; Pocker Y., Ciula J. C. (1989) J. Am. Soc.111: 4728; Waldmann H. (1991) Angew. Chem.103; 1335 [Int. (1991)30: 1306]; Forman M. A., Dailey W. P. (1991) J. Am. Chem. Soc.113: 2761; Ipaktschi J., Heydari A. (1992) Angew. Chem.104: 335 [Int. (1992)31: 313]
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Gössinger, E., Graupe, M. & Zimmermann, K. Untersuchungen zur Synthese des Nodusmicin, I: Darstellung von (±)-(1R*,5R*,6R*,7S*8R*,9R*,10R*)-5-Acetyl-7,9-dibenzyloxy-10-hydroxy-8-methylbicyclo[4.4.0]decan-3-on. Monatsh Chem 124, 965–979 (1993). https://doi.org/10.1007/BF00816420
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DOI: https://doi.org/10.1007/BF00816420