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Base‐Induced Decarboxylation of Polyunsaturated α ‐Cyano Acids Derived from Malonic Acid: Synthesis of Sesquiterpene Nitriles and Aldehydes with β ‐, φ ‐, and ψ ‐End Groups
Author(s) -
Dufossé Laurent,
Cartier Dominique,
Valla Benoist,
Fouillaud Mireille,
Labia Roger,
Valla Alain
Publication year - 2013
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201200162
Subject(s) - chemistry , decarboxylation , malonic acid , moiety , methylene , oxidative decarboxylation , propanoic acid , sesquiterpene , medicinal chemistry , alkene , base (topology) , organic chemistry , stereochemistry , catalysis , mathematical analysis , mathematics
Catalytic base‐induced decarboxylation of polyunsaturated α ‐cyano‐ β ‐methyl acids derived from malonic acid led to the corresponding nitriles 3 ( Schemes 2 and 3 ), 6 ( Scheme 5 ), and 9 ( Scheme 6 ). This decarboxylation occurred with previous deconjugation of the α , β ‐alkene moiety of the α ‐cyano‐ β ‐methyl acid, leading to an α ‐cyano‐ β ‐methylene propanoic acid which was easily decarboxylated (see Scheme 2 ). β ‐Methylene intermediates, in some cases, could be isolated; mechanistic pathways are proposed. The nitriles 3, 6 , and 9 were reduced to the sesquiterpene aldehydes 4 ( β ‐end group), 7 ( φ ‐end group), and 10 ( ψ ‐end group), respectively.