Controlling factors determining the selective HSCN addition to double bonds and their application to the synthesis of 7-isothiocyano-7,8-a-dihydro-bisabolene

Abstract

The reactivity of terminal and trisubstituted double bonds of monoterpenes with HSCN has been examined by GC giving evidence that kinetics is responsible for the chemoselective addition to terminal double bonds in terpenes. The results show that the addition to the terminal double bond is about 17 times faster than for trisubstituted double bonds and that the presence of the first SCN group in the molecule prevents a second addition. The presence of a hydroxyl or methoxy group in the molecule, decreases the reaction kinetics. Based on these kinetic experiments a two steps synthesis of the natural product 7-isothiocyano-7,8-dihydro-alpha-bisabolene using bisabolol as starting material, was planned and successfully accomplished.

Keywords

• terpenes
• HSCN
• double bonds
• chemoselectivity