Denhez Clément, Lameiras Pedro, Berber Hatice
Université de Reims Champagne Ardenne, CNRS, ICMR UMR 7312, 51097 Reims, France.
Org Biomol Chem. 2023 Dec 13;21(48):9572-9582. doi: 10.1039/d3ob01617j.
The conformational behaviour arising from the restricted C(sp)-C(sp) axis in -substituted naphthylcyclohexane and naphthylcyclohexene oxide derivatives of cannabidiol was examined by means of VT-NMR experiments and DFT calculations. Atropisomeric compounds with barriers in the range of 91.1 to 95.1 kJ mol were obtained at 298 K. Two possible transition states (TS1 and TS2) were located, one is more stable depending on the chemical modification made on the monoterpene ring close to the pivot bond. Extended analysis of TS structures to previously reported phenyl derivatives bearing the same -substituent led to similar rotational pathways according to the series: through TS1 in arylcylohexenes and TS2 in arylcyclohexanes. Likewise, conversion of arylcyclohexenes into both series affects the rotation speed by decelerating it, and the nature of the aryl ring seems to have a very minor effect on this phenomenon.
通过变温核磁共振实验和密度泛函理论计算，研究了大麻二酚的β-取代萘基环己烷和萘基环己烯氧化物衍生物中受限的C(sp)-C(sp)轴所产生的构象行为。在298 K下获得了阻转异构化合物，其势垒在91.1至95.1 kJ/mol范围内。确定了两种可能的过渡态（TS1和TS2），根据对靠近枢轴键的单萜环进行的化学修饰，其中一种更稳定。对具有相同β-取代基的先前报道的苯基衍生物的TS结构进行扩展分析，根据该系列得出了类似的旋转途径：芳基环己烯中通过TS1，芳基环己烷中通过TS2。同样，芳基环己烯向两个系列的转化都会通过使其减速来影响旋转速度，并且芳基环的性质似乎对该现象影响很小。
