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Conversion of polyfunctional nitroalkanes into carbonyl compounds synthesis of the pheromone chalcogran and of key building blocks for the macrolides pyrenophorin and vermiculine
Author(s) -
Zschiesche Ruth,
Hafner Thomas,
Reißig HansUlrich
Publication year - 1988
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.198819881211
Subject(s) - chemistry , reagent , nitro , silylation , acetal , cyclopentenone , adduct , diketone , derivative (finance) , organic chemistry , combinatorial chemistry , stereochemistry , catalysis , alkyl , financial economics , economics
Starting from nitroalkane adducts of the general structure 3 , several versions of the Nef reaction are performed. The reagent combination H 2 O 2 /K 2 CO 3 turned out to be the most useful in liberating the carbonyl group because of toleration of acid‐sensitive functionalities. Other methods provide the acetal 5 , diketone 7 , γ‐lactones 8 and 9 , or the chlorinated nitro compound 13 , respectively. Cyclization of the highly functionalized diketone 18 gives cyclopentenone derivative 19 . Trifunctional and tetrafunctional intermediates 12 and 17 can be transformed into 20 and 21 by reduction and silylation. These compounds are known or conceivable precursors for the antibiotic macrolides pyrenophorin and vermiculine, respectively. Nitroalkane 22 affords within a few simple steps the aggregation pheromone chalcogran 24 . The synthetic paths are discussed with regard to efficiency and flexibility.