75022-26-3Relevant academic research and scientific papers
A practical and efficient synthetic route to dihydropipercide and pipercide
Rotherham, Lloyd W.,Edward Semple
, p. 6667 - 6672 (1998)
Dihydropipercide 1 and Pipercide 2 are examples of hydrophobic insecticidal isobutylamide derivatives isolated from Piper Nigrum L. which have received synthetic attention over the past decade. Novel structural features combining the N-isobutyldieneamide array, found in related natural products such as Pellitorine, with the 3,4-methylenedioxyphenyl moiety, found in insecticide synergists including Piperonyl Butoxide and Sesamex, render these as attractive targets for synthesis. Although a variety of synthetic routes to related natural products have appeared in the literature, practical methods for the preparation of the title compounds were lacking. Convenient and convergent 10-11-step protocols were developed which provided access to gram quantities of the targets. Methyl 6-oxohexanoate 4 was prepared from cyclohexanone enol acetate 3 via a tandem ozonolysis, methanolysis, hydrolysis process. Subsequent olefination and olefin isomerization steps followed by further elaboration provided the targets 1 and 2. Noteworthy features of this methodology include the convenient synthesis of oxoester intermediate 4 and the phenythio radical-induced olefin isomerization of intermediate 6 which afforded high yields of >99.5% E-olefin 13. These are both somewhat uncommon but potentially useful processes which may find further application in organic synthesis.
INSECTICIDAL AMIDES. SYNTHESIS OF NATURAL 2(E),4(E),10(E)-PIPERCIDE, ITS 2(E),4(E),10(Z)-STEREOMER, AND RELATED ISOBUTYLAMIDES
Crombie, Leslie,Denman, Raymond
, p. 4267 - 4270 (2007/10/02)
Natural pipercide and its 2(E),4(E),10(Z)-stereomer are synthesised, the latter having superior insecticidal potency and knock down. 10,11-Dihydro- and 10,11-dehydropipercides are also prepared.
