The Fritsch–Buttenberg–Wiechell rearrangement, named for Paul Ernst Moritz Fritsch (1859–1913), Wilhelm Paul Buttenberg, and Heinrich G. Wiechell, is a chemical reaction whereby a 1,1-diaryl-2-bromo-alkenerearranges to a 1,2-diaryl-alkyne by reaction with a strong base such as an alkoxide.[1][2][3][4]
Fritsch–Buttenberg–Wiechell rearrangement
Named after
Paul Ernst Moritz Fritsch Wilhelm Paul Buttenberg Heinrich G. Wiechell
The strong base deprotonates the vinylic hydrogen, which after alpha elimination forms a vinylcarbene. A 1,2-aryl migration forms the 1,2-diaryl-alkyne product. The mechanism of the FBW rearrangement was a subject of on-surface studies where the vinyl radical was visualised with sub-atomic resolution.[6]
Mechanism of the Fritsch-Buttenberg-Wiechell rearrangement
Scopeedit
One study explored this reaction for the synthesis of novel polyynes:[7][8]
^Paul Fritsch (1894). "Ueber die Darstellung von Diphenylacetaldehyd und eine neue Synthese von Tolanderivaten". Justus Liebig's Annalen der Chemie. 279 (3): 319–323. doi:10.1002/jlac.18942790310.
^Buttenberg, W. P. (1894). "Condensation des Dichloracetals mit Phenol und Toluol". Justus Liebig's Annalen der Chemie. 279 (3): 324–337. doi:10.1002/jlac.18942790311.
^Wiechell, H. (1894). "Condensation des Dichloracetals mit Anisol und Phenetol". Justus Liebig's Annalen der Chemie. 279 (3): 337–344. doi:10.1002/jlac.18942790312.
^Rezaei, H.; Yamanoi, S.; Chemla, F.; Normant, J. F. (2000). "Fritsch-Buttenberg-Wiechell Rearrangement in the Aliphatic Series". Org. Lett.2 (4): 419–421. doi:10.1021/ol991117z. PMID 10814340.
^Pavliček, Niko; Gawel, Przemyslaw; Kohn, Daniel R.; Majzik, Zsolt; Xiong, Yaoyao; Meyer, Gerhard; Anderson, Harry L.; Gross, Leo (2018-07-02). "Polyyne formation via skeletal rearrangement induced by atomic manipulation". Nature Chemistry. 10 (8): 853–858. Bibcode:2018NatCh..10..853P. doi:10.1038/s41557-018-0067-y. ISSN 1755-4330. PMC6071858. PMID 29967394.
^One-Pot Formation and Derivatization of Di- and Triynes Based on the Fritsch-Buttenberg-Wiechell Rearrangement Thanh Luu, Yasuhiro Morisaki, Nina Cunningham, and Rik R. Tykwinski J. Org. Chem.2007, 72, 9622–9629 doi:10.1021/jo701810g
Darses, B.; Milet, A.; Philouze, C.; Greene, A. E.; Poisson, J.-F. o., Ynol Ethers from Dichloroenol Ethers: Mechanistic Elucidation Through 35Cl Labeling. Organic Letters 2008, 10 (20), 4445-4447.
January 01, 1970
fritsch, buttenberg, wiechell, rearrangement, named, paul, ernst, moritz, fritsch, 1859, 1913, wilhelm, paul, buttenberg, heinrich, wiechell, chemical, reaction, whereby, diaryl, bromo, alkene, rearranges, diaryl, alkyne, reaction, with, strong, base, such, al. The Fritsch Buttenberg Wiechell rearrangement named for Paul Ernst Moritz Fritsch 1859 1913 Wilhelm Paul Buttenberg and Heinrich G Wiechell is a chemical reaction whereby a 1 1 diaryl 2 bromo alkene rearranges to a 1 2 diaryl alkyne by reaction with a strong base such as an alkoxide 1 2 3 4 Fritsch Buttenberg Wiechell rearrangement Named after Paul Ernst Moritz Fritsch Wilhelm Paul Buttenberg Heinrich G Wiechell Reaction type Rearrangement reaction Identifiers RSC ontology ID RXNO 0000250 The Fritsch Buttenberg Wiechell rearrangement This rearrangement is also possible with alkyl substituents 5 Contents 1 Reaction mechanism 2 Scope 3 See also 4 ReferencesReaction mechanism editThe strong base deprotonates the vinylic hydrogen which after alpha elimination forms a vinyl carbene A 1 2 aryl migration forms the 1 2 diaryl alkyne product The mechanism of the FBW rearrangement was a subject of on surface studies where the vinyl radical was visualised with sub atomic resolution 6 nbsp Mechanism of the Fritsch Buttenberg Wiechell rearrangementScope editOne study explored this reaction for the synthesis of novel polyynes 7 8 nbsp Fritsch Buttenberg Wiechell rearrangement ApplicationSee also editCorey Fuchs reactionReferences edit Paul Fritsch 1894 Ueber die Darstellung von Diphenylacetaldehyd und eine neue Synthese von Tolanderivaten Justus Liebig s Annalen der Chemie 279 3 319 323 doi 10 1002 jlac 18942790310 Buttenberg W P 1894 Condensation des Dichloracetals mit Phenol und Toluol Justus Liebig s Annalen der Chemie 279 3 324 337 doi 10 1002 jlac 18942790311 Wiechell H 1894 Condensation des Dichloracetals mit Anisol und Phenetol Justus Liebig s Annalen der Chemie 279 3 337 344 doi 10 1002 jlac 18942790312 Kobrich G 1965 Eliminations from Olefins Angewandte Chemie International Edition 4 49 68 doi 10 1002 anie 196500491 Rezaei H Yamanoi S Chemla F Normant J F 2000 Fritsch Buttenberg Wiechell Rearrangement in the Aliphatic Series Org Lett 2 4 419 421 doi 10 1021 ol991117z PMID 10814340 Pavlicek Niko Gawel Przemyslaw Kohn Daniel R Majzik Zsolt Xiong Yaoyao Meyer Gerhard Anderson Harry L Gross Leo 2018 07 02 Polyyne formation via skeletal rearrangement induced by atomic manipulation Nature Chemistry 10 8 853 858 Bibcode 2018NatCh 10 853P doi 10 1038 s41557 018 0067 y ISSN 1755 4330 PMC 6071858 PMID 29967394 One Pot Formation and Derivatization of Di and Triynes Based on the Fritsch Buttenberg Wiechell Rearrangement Thanh Luu Yasuhiro Morisaki Nina Cunningham and Rik R Tykwinski J Org Chem 2007 72 9622 9629 doi 10 1021 jo701810g The metal acetylide intermediate is captured by electrophile methyl iodide The reaction product is a biomolecule found in for instance Bidens pilosa Darses B Milet A Philouze C Greene A E Poisson J F o Ynol Ethers from Dichloroenol Ethers Mechanistic Elucidation Through 35Cl Labeling Organic Letters 2008 10 20 4445 4447 Retrieved from https en wikipedia org w index php title Fritsch Buttenberg Wiechell rearrangement amp oldid 1158505315, wikipedia, wiki, book, books, library,
