Cyclotriveratrylene (CTV) is a bowl-shaped molecular scaffold that is commonly employed in supramolecular chemistry for host-guest chemistry and biomimetic molecular recognition, and has been proposed as a vehicle for drug delivery. As part of our research program directed toward the synthesis and application of apex-modified CTV derivatives, we previously reported1 the synthesis of a new ortho-triazaorthocyclophane, N,N',N''-Trimethyltribenzo-1,4,7-triazacyclononatriene via palladium-catalyzed Buchwald-Hartwig N-arylation reactions, and we recently reported mechanistic studies detailing unusual rearrangement chemistry.2 With the goal of developing new medical imaging reagents, we wish to report our recent results of peripheral functionalization of the azacyclophane, including halogenation and subsequent Suzuki coupling chemistry, along with mass spectrometric evidence of metal complexation. In addition, we have observed a Cu(II)-induced oxidative rearrangement to a stable cation radical, as confirmed by X-ray crystallography and characterized by ESR spectroscopy.

Peripheral functionalization and complexation of an ortho-triazacyclophane, N,N',N''-trimethyltribenzo-1,4,7-triazacyclononatriene, and Cu(II)-induced rearrangement to a stable cation radical

248th National Meeting (2014)

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