Abstract
A multi-step route to unsymmetrically substituted benzophenones based on cationic hapto6-arene-hapto5-cyclopentadienyl iron complexes has been developed. The key features are nucleophilic aromatic substitution reactions performed on hapto6-2-chlorocarbomethoxybenzene-hapto5-cyclopentadienyl iron hexafluorophosphate with phenoxides, followed by intramolecular Friedel-Crafts ring-closure. The thus formed xanthone complexes are regioselectively opened, on the iron-coordinated aromatic ring, delivering benzophenone complexes. Regioselective cyanide addition/oxidative demetalation releases heavily substituted benzophenones. A formal total synthesis of the benzophenone appendage of the protein kinase C inhibitor balanol is presented. Xanthones and thioxanthones have been synthesised via nucleophilic aromatic substitution reactions, with phenoxides or thiophenoxides as nucleophiles, performed on hapto6-2-chloro-N,N-diethylbenzamide-hapto5-cyclopentadienyl iron hexafluorophosphate. Photolytic decomplexation followed by Directed remote Metalation delivers the heterocycles. A new synthetic method for the preparation of diaryl selenides based on nucleophilic aromatic substitution reactions performed on hapto6-chloroarene transition metal complexes has been developed. The preparation of hapto6-trifluoromethanesulphonylbenzene-hapto5-cyclopentadienyl iron hexafluorophosphate and its reactivity in SNAr reactions or palladium-catalysed trans-formations is described.
Original language | English |
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Qualification | Doctor |
Awarding Institution |
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Award date | 2000 Nov 24 |
Publisher | |
ISBN (Print) | 91-7874-081-9 |
Publication status | Published - 2000 |
Bibliographical note
Defence detailsDate: 2000-11-24
Time: 10:15
Place: Centre for Chemistry and Chemical Engineering
External reviewer(s)
Name: Stephenson, G. Richard
Title: Dr
Affiliation: University of East Anglia, Norwich, U.K.
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Article: I Nilsson, J. P.; Andersson, C.-M.A Divergent Route to Substituted Benzophenones Based on Cationic h6-(Arene)iron IntermediatesTetrahedron Lett. 1997, 38, 4635-4638.
Article: II Storm, J. P.; Andersson, C.-M.An Organoiron Approach to the Benzophenone Appendage of the Protein Kinase C Inhibitor BalanolOrg. Lett. 1999, 1, 1451-1453.
Article: III Storm, J. P.; Andersson, C.-M.Iron-Mediated Synthetic Routes to Unsymmetrically Substituted, Sterically Congested BenzophenonesJ. Org. Chem. 2000, 65, 5264-5274.
Article: IV Vasil'ev, A. A.; Engman, L.; Storm, J. P.; Andersson, C.-M.Preparation of Unsymmetrical Diaryl Selenides via SNAr Reactions in h6-Chloroarene Transition Metal ComplexesOrganometallics 1999, 18, 1318-1325.
Article: V Storm, J. P.; Ionescu, R. D.; Martinsson, D.; Andersson, C.-M.A New Route to Xanthones and Thioxanthones Based on h6-2-Chloro-N,N-Diethylbenzamide-h5-Cyclopentadienyl Iron HexafluorophosphateSynlett 2000, 975-978.
The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
Subject classification (UKÄ)
- Organic Chemistry
Free keywords
- Directed remote Metalation
- nucleophilic aromatic addition
- nucleophilic aromatic substitution
- Arene-iron complexes
- balanol
- Organic chemistry
- Organisk kemi