A series of propeller‐shaped, C3‐symmetric cyclophanes have been synthesized by the macrocyclization of 1,3,5‐trimercaptobenzene (12) with either a tris[o‐(halomethyl)aryl]phosphine (e.g. 11) or a tris[o‐(halomethyl)aryl]benzene (e.g. 24). Two phosphine‐capped cyclophanes (5 and 6) were prepared in this way; they proved to be configurationally stable, and both were resolved into pure enantiomers by supercritical fluid chromatography on chiral supports. Compound 6, in particular, displayed a large specific rotation ([α]D ≈ 800) and strong circular dichroism. The one triarylbenzene‐capped cyclophane (9) that was made possessed a modest barrier to racemization (ΔGrac‡ = 15.7 kcal/mol). Computational studies of the trends in optical rotation for this class of compounds as well as the pathway for the racemization of 9 are also reported.
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