Synthesis and Solid-State Dynamics of a Crystalline Steroid Molecular Rotor without the Alkyne Axle: Steroid Dimers Based on a 1,4-Di(1,3-dioxan-2-yl)benzene Moiety

Two diastereomeric crystalline steroid
dimers were obtained by
acid-catalyzed double acetalization of (20S)-5α-pregnan-3β,16β,20-triol
3-monoacetate with terephtalaldehyde. These compounds were characterized
by NMR in solution, MS, single-crystal X-ray diffraction, and variable-temperature
solid-state NMR by 13C cross-polarization magic angle spinning
(CPMAS). While the phenylene rotator in the SR diastereomer remains static even at 373 K, the RR isomer shows a slow rotational process of
the phenylene ring at temperatures above room temperature and thus
may be considered the first crystalline steroid molecular rotor without
the alkyne axle.