Synthesis and Reactivity of (+)-16-Deoxo-15-oxoisosteviol

Abstract

The synthesis of optically pure (-)-isosteviol derivatives with a keto function shifted to position 15 and its insertive esterification are described.

Key words

terpenoids - chiral pool - esters - carbocycles - rearrangements

References

• 1 Starraat AN. Kirby CW. Pocs R. Brandle JE. Phytochemistry  2002,  59:  367 
• 2a Mosettig E. Nes WR. J. Org. Chem.  1955,  20:  884 
• 2b Mosettig E. Beglinger U. Dolder F. Lichti H. Quitt P. Waters JA. J. Am. Chem. Soc.  1963,  85:  2305 
• 3 Alfonsov VA. Bakaleynik GA. Gubaidullin AT. Kataev VE. Kovyljaeva GI. Konovalov AI. Litvinov IA. Strobykina IYu. Andreeva OV. Korochkina MG. Mendeleev Commun.  1999,  6:  227 
• 4 Bomkamp M. Artiukhov A. Kataeva O. Waldvogel SR. Synthesis  2007,  1107 
• 5a Waldvogel SR. Fröhlich R. Schalley CA. Angew. Chem. Int. Ed.  2000,  39:  2472 
• 5b Bomkamp M. Siering C. Landrock K. Stephan H. Fröhlich R. Waldvogel SR. Chem. Eur. J.  2007,  13:  3724 
• 6a Schopohl MC. Siering C. Kataeva O. Waldvogel SR. Angew. Chem. Int. Ed.  2003,  42:  2620 
• 6b Schophol MC. Faust A. Mirk D. Fröhlich R. Kataeva O. Waldvogel SR. Eur. J. Org. Chem.  2005,  2987 
• 7 Fabris F. Zambrini L. Rosso E. De Lucchi O. Eur. J. Org. Chem.  2004,  15:  3313 
• 8 Coates MC. J. Org. Chem.  1987,  52:  2065 
• 9 Rabjohn N. Org. React.  1976,  24:  261 
• 10 Cram DJ. Sahyun MRV. J. Am. Chem. Soc.  1962,  84:  1734 
• 11 Caglioti L. Tetrahedron  1966,  22:  487 
• 12 Frey B. Schnaubelt J. Reißig H.-U. Eur. J. Org. Chem.  1999,  1385 
• 13a Waldvogel SR. Mirk D. Tetrahedron Lett.  2000,  41:  4769 
• 13b Waldvogel SR. Mirk D. Herbrüggen J. GDCh-Monographie  2001,  23:  233 
• 15 Alfonsov VA. Andreeva OV. Bakaleynik GA. Beskrovny DV. Kataev VE. Kovyljaeva GI. Litvinov IA. Militsina OI. Strobykina IYu. Mendeleev Commun.  2003,  13:  234 
• 16 Alfonsov VA. Andreeva OV. Bakaleynik GA. Beskrovny DV. Gubaidullin AT. Kataev VE. Kovyljaeva GI. Konovalov AI. Korochkina MG. Latypov ShK. Litvinov IA. Musin RZ. Strobykina IYu. Russ. J. Gen. Chem.  2003,  73:  1119 
• 17 Nishio M. Hirota M. Umezawa Y. The CH/π Interaction: Evidence, Nature and Consequences   Wiley-VCH; New York: 1998. 
• 18 Otwinowski Z. Minor W. Methods Enzymol.  1997,  276:  307 
• 19 Otwinowski Z. Borek D. Majewski W. Minor W. Acta Crystallogr. A  2003,  59:  228 
• 20 Sheldrick GM. Acta Cryst.  1990,  A46:  467 

14

Tested reaction conditions for the synthesis of 8: (+)-Methyl-ent-15-oxobeyeran-19-oate (6) was dissolved in toluene, chlorobenzene or 1,2-dichlorobenzene and, after addition of catechol and a catalytic amount of a Brønsted acid, the mixture was heated under reflux applying a Dean-Stark trap. Even under very harsh conditions such as TsOH in boiling 1,2-dichlorobenzene (180 °C) or TfOH in boiling toluene, no product formation was observed.

21

G. M. Sheldrick; Universität Göttingen, 1997.