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• W2124607048 abstract "Gemäß einem allgemeinen Reaktionsschema reagieren o-Lithioarylester 4a, b, -amide 13a, b, 17b und -amidine 39b von nicht enolisierbaren Carbonsäuren ebenso wie ein entsprechendes Diphenylphosphinsäureamid 51b unter milden Bedingungen zu den intensiv gefärbten Lithiumderivaten von o-Acylphenolen 6a, b und o-Acylarenaminen 15a, b, 18a, 41a, 52a, die abschließend zu den Neutralprodukten 7a, b, 14a, b, 18b, 41b, 52b hydrolysiert werden. Die lithiierten Umlagerungsvorstufen werden dabei meist über Halogen-Metall-Austauschreaktionen hergestellt. Im Falle des N,N-Di-p-tolylpivalamids 33 kann eine derartige [1,3]-Umlagerung auch über direkte Metallierung des Edukts induziert werden. In N-Methyl-N-phenylpivalamid (29) hingegen erfolgt ausschließliche Metallierung der N-Methylgruppe, der sich eine [1,2]-Wanderung des Pivaloylrestes anschließt. Auch Silylgruppen können analoge [1,3]-Verschiebungen erfahren, wie die Umwandlung des o-lithiierten N-(Trimethylsilyl)anilins 63b zu den o-Silylanilinen 65a, b belegt. Läßt man eine Benzoyl- und eine Sulfonylgruppe um die [1,3]-Verschiebung konkurrieren, wie im N-tosylierten Benzamid 47b, so wandert nur der Benzoylrest. Die Wanderungstendenz des Trimethylsilylrestes hingegen kommt der einer Benzoylgruppe gleich, wie anhand des N-silylierten Benzamids 66b gezeigt wurde. Carbanionically Induced [1,3]-migrations of π- and Coordinatively Unsaturated Groups According to a general reaction scheme, o-lithioaryl esters 4a, b, amides 13a, b, 17b, and amidines 39b of non-enolizable carboxylic acids as well as a corresponding diphenylphosphinic amide 51b react under mild conditions to give the intensely coloured lithium derivatives of o-acylphenoles 6a, b and o-acylarenamines 15a, b, 18a, 41a, 52a, which are finally hydrolyzed to the neutral products 7a, b, 14a, b, 18b, 41b, 52b, respectively. The lithiated precursors of the rearrangement are mostly prepared by halogen/metal exchange reactions. In the case of N,N-di-p-tolylpivalamide 33 such a [1,3]-rearrangement also could be induced by direct metalation of the educt. With N-methyl-N-phenylpivalamide (29), however, exclusive metalation of the N-methyl group occurs, followed by [1,2]-migration of the pivaloyl group. Silyl groups, too, can undergo analogous [1,3]-shifts, as was demonstrated by the rearrangement of the o-lithiated N-(trimethylsilyl)aniline 63b to the o-(trimethylsilyl)anilines 65a, b. When a benzoyl and a sulfonyl group can compete for the [1,3]-shift, as in the N-tosylated benzamide 47b, only the benzoyl group migrates. However, the migration tendency of the trimethylsilyl group equals that of the benzoyl group as was shown with the N-silylated benzamide 66b." @default.
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• W2124607048 date "1983-10-01" @default.
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• W2124607048 title "Carbanionisch induzierte [1,3]‐Wanderungen π‐ und koordinativ ungesättigter Gruppen" @default.
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• W2124607048 doi "https://doi.org/10.1002/cber.19831161014" @default.
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