EFFECTS OF SUBSTITUENTS ON CH BOND DISSOCIATION ENTHALPIES OF ENT-KAURANE DITERPENOIDS: A DFT STUDY

Abstract

C-H bond dissociation enthalpies (BDEs) of seven ent-kaurane diterpenoids extracted from Croton tonkinensis Gagnep. have been investigated by using density functional theory (DFT) method. The calculations were performed at the M05-2X/6-31+G(d) level of theory. Additionally, insight into the effects of different substituents including –NH2, –OH, –NO2, –SH, –CN, –Cl, –CONH2, –CH-(CH3)2, –NHCOCH3, –OCOCH3 and –C2H5 on BDE have also been provided. The results showed that the BDE value of ent-16(S)-18-acetoxy-7b-hydroxykaur-15-one compound is lowest, being 83.5 kcal/mol. Among substituents binding at C16 position of this molecule, –NH2 has the most remarkable influence on the BDE (C-H) value. Indeed, the BDE of C16-H significantly decreases from 83.5 to 68.4 kcal/mol when replacing –CH3 group by –NH2 one at the C16 position. The obtained results may provide more information for organic synthesis of ent-kaurane based – novel antioxidant compounds.