Stereoselective Synthesis and Physicochemical Properties of Liquid‐Crystal Compounds Possessing a trans‐2,5‐Disubstituted Tetrahydropyran Ring with Negative Dielectric Anisotropy

Three stereoselective syntheses and the physicochemical properties of trans,trans‐5‐(4‐ethoxy‐2,3‐difluorophenyl)‐2‐(4‐propylcyclohexyl)tetrahydropyran, which is an important liquid‐crystal compound with a large negative dielectric anisotropy (Δε=?7.3), are described. The key step in the construction of the trans‐2,5‐disubstituted tetrahydropyran ring in the first approach involved a benzylic cation mediated intramolecular olefin cyclization of a 2‐allyloxy‐1‐arylethanol derivative. The second method included the Et₂Zn‐induced 1,2‐aryl shift of a bromohydrin obtained from a hetero‐Diels–Alder reaction, followed by stereoselective bromination. The third approach utilized the hetero‐Diels–Alder reaction of trans‐4‐propylcyclohexanecarboxaldehyde and a 2‐aryl‐3‐(trimethylsilyl)oxy‐1,3‐butadiene, followed by stereoselective protonation. From results obtained by using a quantum chemical calculation method, the reason why the target compound shows a large negative Δε value is discussed.