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Self-Assembly of a Trithioorthoformate-Capped Cyclophane and Its Endohedral Inclusion of a Methine Group |
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| Authors: | Mary S Collins Trevor A Shear Elizabeth K Smith Dr S Michael Strain Dr Lev N Zakharov Prof Dr Darren W Johnson |
| Institution: | 1. Department of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon, 97403-1253 USA;2. CAMCOR—Center for Advanced Materials Characterization in Oregon, University of Oregon, Eugene, Oregon, 97403-1443 USA |
| Abstract: | 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. |
| Keywords: | cyclophanes dynamic covalent chemistry self-assembly supramolecular chemistry trithioorthoformate |