Financial support from GlaxoSmithKline, the ERDF (IS:CE-Chem & InterReg IVa) and the EPSRC (including support for the Iridis cluster) are gratefully acknowledged. Rob Wheeler and Andy Craven are thanked for valuable advice.
An Efficient Flow-Photochemical Synthesis of 5H-Furanones Leads to an Understanding of Torquoselectivity in Cyclobutenone Rearrangements†
Article first published online: 22 MAR 2012
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 51, Issue 18, pages 4405–4408, April 27, 2012
How to Cite
Harrowven, D. C., Mohamed, M., Gonçalves, T. P., Whitby, R. J., Bolien, D. and Sneddon, H. F. (2012), An Efficient Flow-Photochemical Synthesis of 5H-Furanones Leads to an Understanding of Torquoselectivity in Cyclobutenone Rearrangements . Angew. Chem. Int. Ed., 51: 4405–4408. doi: 10.1002/anie.201200281
- Issue published online: 24 APR 2012
- Article first published online: 22 MAR 2012
- Manuscript Revised: 6 MAR 2012
- Manuscript Received: 11 JAN 2012
- density functional calculations;
- small ring systems
Go with the flow: 4-Hydroxycyclobutenones were efficiently transformed into 5H-furanones using an inexpensive flow-photochemical setup. The results challenge the notion that this and the related thermochemical rearrangement display torquoselectivity in their electrocyclic opening to a vinylketene intermediate. Selectivity in the photochemical rearrangement is due a dichotomous reactivity of the (E)- and (Z)-vinylketene intermediates (see scheme).