Probing the stereochemical structure of carenes using Raman and Raman optical activity spectroscopy

The great interest in terpene compounds such as 2-, 3- and 4-carene is due to their undeniable biological activity. However, in recent years, there has been increasing interest in carenes in the context of biofuels. The current growing and insatiable demand for petroleum fuels creates an area for alternative biofuels. Research shows that natural products, which contain compounds from the carenes family, such as pine oil or turpentine (3-carene can constitute up to 70% of the composition of turpentine), can be successfully used as biofuels or additives in biofuels. In this work, both experimental and calculated (DFT/B3LYP/aug-cc-pVDZ) Raman and ROA (Raman optical activity) spectra of 1S,3R-cis-4-carene and 1S,3S-trans-4-carene were reported and analyzed for the first time. Then these spectra were compared with Raman and ROA spectra of other chiral members of the carenes family (1S-2-carene and 1S-3-carene). This knowledge about the spectra of individual carenes made it possible to identify (+)-1S-3-carene in selected samples of pine essential oil from the needles of Pinius sylvestris (Scots pine).