Isocyanurates with Planar Chirality: Design,Optical Resolution,and Isomerization

Designs and syntheses of isocyanurates ( 1–3 ) are described on the basis of a novel concept that two enantiotopic faces of C_s‐symmetric, prochiral planar molecules are differentiated with a location of groups at the top or bottom of the planar skeleton using a rigid linker. Such isocyanurates are atropisomeric. The planar‐chiral structures of 1 and 2 _anti (anti‐conformer of 2 ) were confirmed by single‐crystal X‐ray analyses, and the space groups were P1 (for 1 ) and P2₁/c (for 2 _anti), resulting that the crystals were racemates. Optical resolutions of 1–3 were successfully accomplished by using chiral high‐performance liquid chromatography technique in combination with circular dichroism, absorption, and nuclear magnetic resonance spectroscopies and mass spectrometry. Furthermore, the rotational barriers (ΔG^?s) related to isomerizations of 1–3 were estimated to be 27.2 (for 1 at 50 °C), 27.6 (for 2 _anti at 50 °C), and 40.6 (for 3 _syn at 150 °C) kcal/mol. The ΔG^?s of 2 and 3 were higher than that of 1 and, in particular, that of 3 was highest among them. This result indicates that an introduction of bulky substituents and an intramolecular bridging are effective for inhibitions of the isomerizations. Chirality 00:000–000, 2012. © 2012 Wiley Periodicals, Inc.