Enantioselective syntheses of (+)-xylarenal A and ent-xylarenal A.
[reaction: see text] The total synthesis of the sesquiterpenoid xylarenal A is reported. This first synthetic entry to an eremophilane terpenoid with an exocyclic vinyl aldehyde unit involves the use of the bicyclic enone (+)-3, which after a gamma-oxidation and alpha'-allylation leads to the formation of the ketone (+)-8. After its acylation, an oxidative cleavage of the allyl side chain followed by alpha-methylenation of the resulting aldehyde gives (+)-xylarenal A (1). The synthesis of (-)-xylarenal A from (-)-3 is also reported. Moreover, the first total synthesis of the trinoreremophilane (+)-1alpha-hydroxyisoondetianone (5) is described.
Díaz
Sandra
S
Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, Av. Joan XXIII s/n, 08028 Barcelona, Spain.
González
Asensio
A
Bradshaw
Ben
B
Cuesta
Javier
J
Bonjoch
Josep
J
D002384:Catalysis; D005658:Fungi / Q000737:chemistry; D007202:Indicators and Reagents; D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D013237:Stereoisomerism
D007202:Indicators and Reagents; D012717:Sesquiterpenes; C470215:xylarenal A