ISSN:
0009-2940
Schlagwort(e):
7-Oxonorbornane-2,3-dicarboximides
;
Reductive amination
;
4,7-Methanoisoindoles
;
Chemistry
;
Inorganic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Ozonizations of several 7-isopropylidenenorbornane-2,3-dicarboximides (2, 10) yield 7,7-dihydroxynorbornane-2,3-dicarboximides (3, 11) and/or 7-oxonorbornane-2,3-dicarboxi-mides (4, 12). Dehydration of the dihydroxy derivatives to the corresponding carbonyl compounds can be carried out by reaction with P2O5 in an aprotic solvent. Reaction of hydrates 3 with methanol gives mixtures of the stereoisomeric hemiacetals 13 and 14, whereas reaction with other nucleophiles give only the stereoisomer derived from attack by the less hindered carbonyl face. Thus NaBH4 or Al(iPRO)3 reduction of 3 or 4 yields alcohols 15 and LiAlH4 reduction of 3 or 4 amino alcohols 16. Reaction of 4b with phenylmagnesium bromide gives alcohol 22 and a direaction product (rac-26) that easily dehydrates to a tetracyclic compound (rac-30). Reductive aminations of 3 or 4 lead to amines 19 directly or via imines rac-20 and amines 23. LiAIH4 reduction of amine 23b affords tricyclic compounds (rac-27) and (rac-28). The last one was converted to diamine 24 by reduction with NaBH3CN. Similarly, amine 21 was converted into diamine 25, partially via aminal 29 as intermediate. The structures of compounds 3b, 19a, rac-27, and rac-30 have been established by X-ray diffraction analysis.
Zusätzliches Material:
5 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/cber.19941271018
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