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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
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
external identifiers
  • Other:ISRN: LUNDL/NKOK-1042-SE
ISBN
91-7874-081-9
language
English
LU publication?
yes
id
02c8f351-9a72-4944-8d44-4072b9ff6cb5 (old id 40938)
date added to LUP
2007-10-14 17:06:52
date last changed
2016-09-19 08:45:04
@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},
  keyword      = {Directed remote Metalation,nucleophilic aromatic addition,nucleophilic aromatic substitution,Arene-iron complexes,balanol,Organic chemistry,Organisk kemi},
  language     = {eng},
  pages        = {50},
  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},
}