A practical asymmetric synthesis of trans-4,5-benzhydrindan-1-ones as a precursor of A-nor B-aromatic steroidal compounds

Journal of Organic Chemistry

Volumn 70, Issue 17, 2005, Pages 6898-6903

  Matsuya, Yuji ^a   Masuda, Seiji ^a   Itoh, Takakatsu ^a   Murai, Taiki ^a   Nemoto, Hideo ^a  

^a UNIVERSITY OF TOYAMA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; DERIVATIVES; SYNTHESIS (CHEMICAL);

ASYMMETRIC SYNTHEIS; BENZOCYLOBUTENE; STEROIDAL COMPOUNDS; THERMAL CLEAVAGE;

AROMATIC COMPOUNDS;

2 ISOPROPYLIDENEGLYCEROKETONE DERIVATIVE; 2 QUINODIMETHANE DERIVATIVE; 4,5 BENZHYDRINDAN 1 ONE DERIVATIVE; AROMATIC COMPOUND; BENZOCYCLOBUTENE DERIVATIVE; FUSED ALICYCLIC AROMATIC COMPOUND; KETONE; MANNITOL; QUINONE DERIVATIVE; STEROID; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; CHIRALITY; CYCLOADDITION; DEGRADATION; DIASTEREOISOMER; GRIGNARD REACTION; HEAT TREATMENT; PRECURSOR; STEREOCHEMISTRY; STEROIDOGENESIS;

BENZENE DERIVATIVES; STEREOISOMERISM; STEROIDS;

EID: 23644458565     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo051060w     Document Type: Article

References (31)

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12. While the product 9 afforded a corresponding ketone upon treatment with PDC, the isomeric side product gave an aldehyde by the same oxidation, which supported the structure determination of the acetonides.
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15. The product 2a obtained from these manipulations was transformed into the final compound 5a, which showed no optical rotation.
16. D value of the final compound 5a synthesized from 2a thus obtained was +93.5 (c 0.4, MeOH).
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25. Considerations of these reaction models are described in the previous papers: see refs 15a-c.
26. With regard to a different trend of the stereoselectivity between the ketones utilized here and the corresponding aldehyde, higher Lewis basicity of the ketone carbonyl groups compared to that of the aldehyde may affect the stereochemical outcome.
27. Preparative methods for compounds 15 and 16 are provided in the Supporting Information.
28. Although the relative configurations of the adducts 17 and 18 were deduced on the basis of the empirical rule (Landmann, B.; Hoffmann, R. W. Chem. Ber. 1987, 120, 331-339), those of 3a and 3b were determined by NOE experiments after conversion to 4 (ref 3).
29. The analytical condition for the determination of the optical purity of 5a using HPLC has been described in ref 3.
30. The optical purity of product 5c (91% ee) was somewhat lower than expected. This may be attributed to a partial loss of the optical purity of (R)-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde used during the preparation or the reaction with the acetylide.
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