6909-37-1Relevant articles and documents
Photochemical Unmasking of Polyyne Rotaxanes
Woltering, Steffen L.,Gawel, Przemyslaw,Christensen, Kirsten E.,Thompson, Amber L.,Anderson, Harry L.
supporting information, p. 13523 - 13532 (2020/09/02)
Bulky photolabile masked alkyne equivalents (MAEs) are needed for the synthesis of polyyne polyrotaxanes, as insulated molecular wires and as stabilized forms of the linear polymeric allotrope of carbon, carbyne. We have synthesized a novel MAE based on phenanthrene and compared it with an indane-based MAE. Photochemical unmasking of model compounds was studied at different wavelengths (250 and 350 nm), and key products were identified by NMR spectroscopy and X-ray crystallography. UV irradiation at 250 nm leads to unmasking of both MAEs. Irradiation of the phenanthrene system at 350 nm results in quantitative dimerization via [2 + 2] cycloaddition to form a [3]-ladderane; irradiation of this ladderane at 250 nm generates a dihydrotriphenylene, which can be oxidized easily to a triphenylene. Irradiation of the indane-based MAE at 350 nm in the presence of traces of oxygen forms an endoperoxide and a bisepoxide. Both MAEs have been incorporated into rotaxanes via copper-mediated active metal template Glaser or Cadiot-Chodkiewicz coupling. The identity of the rotaxanes was confirmed by NMR spectroscopy and mass spectrometry. The phenanthrene rotaxane decomposes during attempted photochemical unmasking, whereas photolysis of the indane rotaxane results in unmasking of the polyyne thread to form a rotaxane with a chain of 16 sp-hybridized carbon atoms. This approach opens avenues toward the synthesis of encapsulated carbon allotropes.
Chemistry of 2-Carbenabicyclooctadiene
Freeman, Peter K.,Swenson, Karl E.
, p. 2033 - 2039 (2007/10/02)
Pyrolytic decomposition of the lithium or potassium salt of the tosylhydrazone of bicycloocta-3,6-dien-2-one (11) or photolysis of the lithium salt of 11 results in the formation of bicycloocta-2,6-diene (12), tricyclo2,7>oct-3-ene (13), tetracyclo2,8.04,6>octane (14), semibullvalene (15), 5-ethynyl-1,3-cyclohexadiene (16), and endo-6-ethynylbicyclohex-2-ene (17).The formation of the C8H8 fraction (15-17) is ascribed to insertion and rearrangement reactions of singlet 2-carbenabicyclooctadiene, whereas the formation ofthe C8H10 fraction (12-14) appears to be the result of hydrogen abstraction reactions of the corresponding triplet carbene or closely related species.
