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Oxidation of o-Isopropylphenol with Lead Tetraacetate: 
Synthesis of the Unit of Celastroidin Terpenes 
by the Diels-Alder Condensation 
by C.K. Jankowski1, A. Savoie1, D. Lesage1, J. Boivin1, G. Leclair1, E. Diaz T.2, R. 
Reyes-Chilpa2, M. Jimenez-Estrada2 and H. Barrios2 
1Département de chimie et biochimie, Université de Moncton, Moncton, NB, E1A 3E9, Canada 
2Instituto de Quimica, UNAM, Cd Universitaria, Circuito Exterior, 04510 Mexico, DF, Mexico 
(Received October 15th, 2004) 
Lead tetraacetate oxidation of o-isopropyl phenol under various conditions led to the 
dienone acetate which, when dimerized, represents a central part of the celastroidin 
penta- and hexa-terpenes (natural products from the Mexican shrub Hippocratea 
Celastroides). Six oxidation products formed in this reaction (the iso-propyl dienolone 
acetate, two dimers, benzoquinone, and two phenol acetates) were identified with help of 
2D and 3D NMR, GC and LC-MS. From this, we concluded that the dimer skeleton observed 
for the dienolone acetate in natural products corresponded to the product from the 
photochemical pathway, and that the synthetic dimer has the opposite geometry; this was 
verified by molecular modelling. The oxidation of the second compound, o-cresol, leads 
to a similar profile of products. 
Key words: Diels-Alder on dienones, phenol Wessely oxidation, Diels-Alder in plant, 
Hippocratea dimeric diterpenes 
Polish J. Chem., 79, 429–440 (2005)

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2005 oxidation...celastroidin

  • 1. Oxidation of o-Isopropylphenol with Lead Tetraacetate: Synthesis of the Unit of Celastroidin Terpenes by the Diels-Alder Condensation by C.K. Jankowski1, A. Savoie1, D. Lesage1, J. Boivin1, G. Leclair1, E. Diaz T.2, R. Reyes-Chilpa2, M. Jimenez-Estrada2 and H. Barrios2 1Département de chimie et biochimie, Université de Moncton, Moncton, NB, E1A 3E9, Canada 2Instituto de Quimica, UNAM, Cd Universitaria, Circuito Exterior, 04510 Mexico, DF, Mexico (Received October 15th, 2004) Lead tetraacetate oxidation of o-isopropyl phenol under various conditions led to the dienone acetate which, when dimerized, represents a central part of the celastroidin penta- and hexa-terpenes (natural products from the Mexican shrub Hippocratea Celastroides). Six oxidation products formed in this reaction (the iso-propyl dienolone acetate, two dimers, benzoquinone, and two phenol acetates) were identified with help of 2D and 3D NMR, GC and LC-MS. From this, we concluded that the dimer skeleton observed for the dienolone acetate in natural products corresponded to the product from the photochemical pathway, and that the synthetic dimer has the opposite geometry; this was verified by molecular modelling. The oxidation of the second compound, o-cresol, leads to a similar profile of products. Key words: Diels-Alder on dienones, phenol Wessely oxidation, Diels-Alder in plant, Hippocratea dimeric diterpenes Polish J. Chem., 79, 429–440 (2005)