Issue 12, 2015

Non-decarbonylative photochemical versus thermal activation of Bu4N[Fe(CO)3(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes

Abstract

The base metal complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed at room temperature. Spectroscopic investigations show that the metal carbonyl catalyst is not decarbonylated. The best performance was observed at a wavelength of 415 nm. icMRCI+Q analysis of the excited singlet and triplet states of the [Fe(CO)3(NO)] anion was performed and used to calculate the vertical excitation energies which are in good agreement with the experimental data. CASSCF analysis indicates that the Fe center in all excited states of the ferrate becomes more electrophilic while adopting a distorted tetrahedral configuration. Both aspects have a positive synergistic effect on the formation of the initial π-complex with the incoming organic substrate.

Graphical abstract: Non-decarbonylative photochemical versus thermal activation of Bu4N[Fe(CO)3(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Jun 2015
Accepted
02 Sep 2015
First published
03 Sep 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2015,6, 7034-7043

Author version available

Non-decarbonylative photochemical versus thermal activation of Bu4N[Fe(CO)3(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes

C. Lin, D. Pursley, J. E. M. N. Klein, J. Teske, J. A. Allen, F. Rami, A. Köhn and B. Plietker, Chem. Sci., 2015, 6, 7034 DOI: 10.1039/C5SC02342D

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