First diastereoselective synthesis of (-)-thyrsiflorin a methyl ester

Synlett

Volumn , Issue 5, 1997, Pages 574-576

  Abad, Antonio ^a   Agulló, Consuelo ^a   Arnó, Manuel ^a   Marín, M Luisa ^a   Zaragozá, Ramón J ^a  

^a UNIVERSITY OF VALENCIA   (Spain)

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[No Author keywords available]

Indexed keywords

EID: 0002541971     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1997-3217     Document Type: Article

References (29)

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11. Several synthetic routes to the obtention of related podocarpenones have been reported: ApSimon, J.W.; Fyfe, K.E.; Greaves, A.M. Total Synthesis of Natural Products; ApSimon, J. Ed.; Wiley: New York, 1984; Vol. 6, pp 85-139.
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19. 2, to give the oxonium ion ii. This intermediate evolves by migration of C-O bond to give a carbocation which by elimination of a proton gives, after work-up, diene 13. It is interesting to note that C ring of this mentioned diene prefers a boat conformation in which C-17 methyl group is axial. Both molecular mechanics calculations (PCModel) and spectroscopic data (NOEdif) supported this geometry. (Chemical Presented)
20. Ray, C.; Saha, B.; Ghatak, U.R. Tetrahedron 1990, 46, 2857.
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24. Experimental procedure: To a refluxing solution of bis(N-t- butylsalicylaldiminato) copper (II) (24 mg, 0.06 mmol) in toluene (30 ml), a solution of the diazoketone 5 (237 mg, 0.64 mmol) in toluene (10 ml) was added slowly over 6 h. After the addition was complete, the reaction mixture was stirred for a further 30 min., and then solvent removed under reduced pressure. The crude product was purified by chromatography (20% ethyl acetate-petrol) to give the ketal 6 (180 mg, 82%).
25. a) Lafontain, J.; Mongrain, M.; Sergent-Guay, M.; Ruest, L.; Deslongchamps, P. Can. J. Chem. 1980, 58, 2460.
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28. 3OH/HCl afforded, as the sole identifiable product, the mixture of keto-esters 14. This fact can be explained by the following mechanism: first of all hydrolysis of the ketal moiety followed by cleavage of the cyclopropane ring is observed. Then, hemiketalization of the carbonyl group at C-15 of the resulting enone 12 and further retro-Claisen transformation gives keto-ester 14. (Chemical Presented)
29. 2CO), 38.5 (C-10), 37.1 (C-8), 34.2 (C-14), 33.6 (C-18), 33.1 (C-4), 32.5 (C-1), 32.0 (C-15), 30.0 (C-7), 24.4 (C-16), 23.1 (C-17), 22.0 (C-19), 21.8 (C-6), 18.7 (C-2), and 17.3 ppm (C-20).