Structure elucidation and theoretical investigation of key steps in the biogenetic pathway of schisanartane nortriterpenoids by using DFT methods.

Rubrifloradilactone C (4), a novel bioactive nortriterpenoid, along with four other nortriterpenoids (1-3, 5) were isolated from Schisandra rubriflora. The structure of 4 was determined by extensive NMR spectral analysis, computational evidence by using the GIAO method at the B3LYP/6-311++G(2d,p)//B3LYP/6-31G(d) levels, and X-ray analysis. DFT at the B3LYP/6-311+G(d,p) level was selected to clarify the key mechanistic steps in the formation of 1 and 4 through transition-state (TS) investigations. The effect of enzymes on the TS barriers was considered by using the polarized continuum model. Other possible products based on the new mechanism were predicted.