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Arene Iron Complexes in Organic Synthesis. New Routes to Benzophenones, Diaryl Selenides, Xanthones and Thioxanthones

Storm, J Peter LU (2000)
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... (More)
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. (Less)
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author
supervisor
opponent
  • Dr Stephenson, G. Richard, University of East Anglia, Norwich, U.K.
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Directed remote Metalation, nucleophilic aromatic addition, nucleophilic aromatic substitution, Arene-iron complexes, balanol, Organic chemistry, Organisk kemi
pages
50 pages
publisher
Organic Chemistry, Lund University
defense location
Centre for Chemistry and Chemical Engineering
defense date
2000-11-24 10:15:00
external identifiers
  • other:ISRN: LUNDL/NKOK-1042-SE
ISBN
91-7874-081-9
language
English
LU publication?
yes
additional info
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)
id
02c8f351-9a72-4944-8d44-4072b9ff6cb5 (old id 40938)
date added to LUP
2016-04-04 10:21:32
date last changed
2018-11-21 20:58:18
@phdthesis{02c8f351-9a72-4944-8d44-4072b9ff6cb5,
  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.},
  author       = {Storm, J Peter},
  isbn         = {91-7874-081-9},
  language     = {eng},
  publisher    = {Organic Chemistry, Lund University},
  school       = {Lund University},
  title        = {Arene Iron Complexes in Organic Synthesis. New Routes to Benzophenones, Diaryl Selenides, Xanthones and Thioxanthones},
  year         = {2000},
}