Leveraging the n-->π* Interaction in Alkene Isomerization by Selective Energy Transfer Catalysis

T. Neveselý, J. J. Molloy, C. McLaughlin, L. Brüss, C. G. Daniliuc and R. Gilmour

Abstract

Fumarate to maleate (E→Z) isomerization was investigated to validate nO→ πC=O* interactions as a driving force for contra-thermodynamic isomerization. A general protocol based on selective energy transfer catalysis was developed with inexpensive thioxanthone as a sensitizer for the conversion of diverse fumarate derivatives, including tetrasubstituted alkenes. The involvement of nO→πC=O* interactions was confirmed by X-ray crystallography.