Arene Iron Complexes in Organic Synthesis. New Routes to Benzophenones, Diaryl Selenides, Xanthones and Thioxanthones
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/40938
- author
- Storm, J Peter LU
- supervisor
- opponent
-
- Dr Stephenson, G. Richard, University of East Anglia, Norwich, U.K.
- organization
- publishing date
- 2000
- 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}},
keywords = {{Directed remote Metalation; nucleophilic aromatic addition; nucleophilic aromatic substitution; Arene-iron complexes; balanol; Organic chemistry; Organisk kemi}},
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}},
}