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. Issue 2 (18th February 2013)

• Record Type: Journal Article
• Authors: Dufossé, Laurent; Cartier, Dominique; Valla, Benoist; Fouillaud, Mireille; Labia, Roger; Valla, Alain
• Is Part Of: Helvetica chimica acta. Volume 96:Issue 2(2013:Feb.)
• Page Start: 259
• Page End: 265
• Publication Date: 2013-02-18
• Subjects: Chemistry -- Periodicals; Chemistry, Analytical -- periodicals; Chimie -- Périodiques; 540
• DOI: 10.1002/hlca.201200162
• Languages: English
• ISSNs: 0018-019X

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Catalytic base‐induced decarboxylation of polyunsaturated <italic>α</italic>‐cyano‐<italic>β</italic>‐methyl acids derived from malonic acid led to the corresponding nitriles <bold>3</bold> (<italic>Schemes 2</italic> and <italic>3</italic>), <bold>6</bold> (<italic>Scheme 5</italic>), and <bold>9</bold> (<italic>Scheme 6</italic>). This decarboxylation occurred with previous deconjugation of the <italic>α</italic>, <italic>β</italic>‐alkene moiety of the <italic>α</italic>‐cyano‐<italic>β</italic>‐methyl acid, leading to an <italic>α</italic>‐cyano‐<italic>β</italic>‐methylene propanoic acid which was easily decarboxylated (see <italic>Scheme 2</italic>). <italic>β</italic>‐Methylene intermediates, in some cases, could be isolated; mechanistic pathways are proposed. The nitriles <bold>3, 6</bold>, and <bold>9</bold> were reduced to the sesquiterpene aldehydes <bold>4</bold> (<italic>β</italic>‐end group), <bold>7</bold> (<italic>φ</italic>‐end group), and <bold>10</bold> (<italic>ψ</italic>‐end group), respectively.</p> </abstract>