Photoinduced functionalization of diterpenes: photochemical behaviour of grandilorolic acid in methanol and acetonitrile

Irradiation of grandiflorolic acid (11) at lambda = 254 nm in acetonitrile gave the two epimers 13 and 14 through a photodecarboxylation reaction of the carboxylic group on C-4. Irradiation of compound 11 in methanol at lambda = 254 nm provided the transformation of the C-20 angular methyl into a carbomethoxymethyl group. In this case, unlike compounds 13 and 14, only one of the two possible isomers (15) was obtained (equatorial methyl at C-4). A mechanistic approach of this reaction in discussed, and the role of mutual stereochemistry between C-20 methyl and C-19 carboxylic group in determining the course of the reaction is pointed out. (C) 2004 Elsevier B.V. All rights reserved.