Intermolecular oxidative dehydrogenative 3,3′-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+; total synthesis of shandougenine B
Wirtanen, T., Muuronen, M., Hurmalainen, J., Tuononen, H., Nieger, M., & Heljala, J. (2016). Intermolecular oxidative dehydrogenative 3,3′-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+; total synthesis of shandougenine B. Organic Chemistry Frontiers, 3(12), 1738-1745. https://doi.org/10.1039/C6QO00331A
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Organic Chemistry FrontiersAuthors
Date
2016Discipline
Epäorgaaninen ja analyyttinen kemiaNanoscience CenterInorganic and Analytical ChemistryNanoscience CenterCopyright
© the Authors, 2016. This journal is © the Partner Organisations 2016. This is an open access article licensed under a Creative Commons Attribution 3.0 Unported Licence.
With an excess of a strong acid, 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ) is shown to promote
metal-free intermolecular oxidative dehydrogenative (ODH) 3,3’-coupling of 2-aryl-benzo[b]furans and
2-aryl-benzo[b]thiophenes up to 92% yield as demonstrated with 9 substrates. Based on the analysis of
oxidation potentials and molecular orbitals combined with EPR, NMR and UV-Vis observations, the
studied reaction is initiated by a DDQ-substrate charge transfer complex and presumably proceeds via
oxidation of the substrate into an electrophilic radical cation that further reacts with another molecule of
a neutral substrate. The coupling reactivity can easily be predicted from the oxidation potential of the substrate
and the morphology of its frontier molecular orbitals. The intermolecular ODH coupling reaction
allowed a concise total synthesis of the natural product shandougenine B.
Publisher
Royal Society of ChemistryISSN Search the Publication Forum
2052-4110Keywords
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Except where otherwise noted, this item's license is described as © the Authors, 2016. This journal is © the Partner Organisations 2016. This is an open access article licensed under a Creative Commons Attribution 3.0 Unported Licence.
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