Preparation of optically active apoverbenone and verbenone from nopinone by use of the sulfenylation-dehydrosulfenylation method. Stability and reactivity attributable to absolute configuration at the sulfur atom in sulfoxides

Journal of Organic Chemistry

Volumn 63, Issue 20, 1998, Pages 6939-6946

  Kosugi, Hiroshi ^a   Ku, Jaseung ^a   Kato, Michiharu ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001166286     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9807316     Document Type: Article

References (28)

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11. In our repeated runs according to the reported procedures, procurement of the bromo ketone 7 was not necessarily reproducible, so that the reproducibility in the overall yield from 1 to 4a appeared to be poor.
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17. Attempted substitution reaction using LDA in place of (diisopropylamino)magnesium bromide proved to be unsuccessful, because the reaction was sluggish and a large portion of 1 was recovered.
18. The products 13b and 19a, b are thermodynamically stable compounds, and their production is attributable to concomitant epimerization of ap-tolylsulfinyl group in the initial products, (35, 5-, (3SA)-, and (3S, Ss)-p-tolyl sulfoxides, for the formation of 13b, 19a, and 19b, respectively.
19. 4 containing pyridine proved to be impractical, because the reaction was sluggish.
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24. Among the products, thermal decomposition products 3, 4a, 17, and 18a were identified by the spectral comparison with authentic samples.
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26. The terms trans and cis refer to whether the substituent points away from (trans) or toward (cis) the gem-dimethyl bridge.
27. 15D = +34.0 (c 1.10, CHC13) and 98% ee, was used.
28. As verbenone is volatile, evaporative removal of toluene from the extract was avoided in the purification step.