Toward the development of a general chiral auxiliary. 5. High diastereofacial selectivity in cycloadditions with trienol silyl ethers: An application to an enantioselective synthesis of (-)-cassioside

Journal of Organic Chemistry

Volumn 61, Issue 23, 1996, Pages 7984-7985

  Boeckman Jr , Robert K ^a   Liu, Yugang ^a  

^a UNIVERSITY OF ROCHESTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CASSIOSIDE; TERPENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS;

EID: 16144365169     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961613q     Document Type: Article

References (28)

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7. Conceptually related studies toward (+)-cassiol were reported during the course of our work: Corey, E. J.; Guzman-Perez, A.; Loh, T.-P. J. Am. Chem. Soc. 1994, 116, 3611.
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14. 4 showed insufficient reactivity.
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16. This conclusion was based upon the observation that reduction of the mixture of diastereomeric cycloadducts 11 and 12 (11:1) afforded a similar mixture of diastereomeric alcohols (∼11:1) of which alcohol 14 was the major isomer. If adducts 11 and 12 were both endo arising from facial selectivity in reaction with the diene, reduction would have led to enantiomers of 14.
17. Details of the single-crystal X-ray analysis of ketone 13 will be published as part of a full account of this work.
18. For reviews, see: (a) Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93, 1503. (b) Schmidt, R. R. Angew. Chem., Int. Ed. Engl. 1986, 25, 212. (c) Paulsen, H. Angew. Chem., Int. Ed. Engl. 1982, 21, 155.
19. For reviews, see: (a) Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93, 1503. (b) Schmidt, R. R. Angew. Chem., Int. Ed. Engl. 1986, 25, 212. (c) Paulsen, H. Angew. Chem., Int. Ed. Engl. 1982, 21, 155.
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22. 2, -78 °C (2 h) → rt (12 h) (96%).
23. 2 and reductive elimination to the α-iodo ketone. This pathway is consistent with the observation that the intermediate α-iodo ketone has the iodine syn to the hydrogen on the β carbon bearing the alkenyl side chain.
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26. 6 as were the characteristics of (+)-cassiol, which was obtained from 14 by sequential acetylation, iodination/elimination, and deprotection. Attempted glycosidation of suitably protected derivatives of (+)-cassiol was unsuccessful in our hands.
27. Ferrier, R. J.; Fumeaux, R. H. Methods Carbohydr. Chem. 1980, 8, 251.
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