Self‐Assembly of a Trithioorthoformate‐Capped Cyclophane and Its Endohedral Inclusion of a Methine Group

An unusual trithioorthoformate‐capped cyclophane cage was assembled via antimony‐activated iodine oxidation of thiols as confirmed by 1H‐NMR spectroscopy and X‐ray crystallography. The disulfide bridges can undergo desulfurization with hexamethylphosphorous triamide (HMPT) at ambient temperature to capture a trithioether cyclophane cage capped by the trithioorthoformate. In both cages a methine proton points directly into the small cavity. This unexpected structure is hypothesized to have formed as a result of haloform insertion during oxidation. Using antimony‐activated iodine oxidation, an unusual trithioorthoformate‐capped disulfide cyclophane cage was synthesized. Sulfur extrusion was shown to be successful, providing the trithioether analogue. Additionally, yield optimization allowed for >58 % yield.