- Palladium-Catalyzed Aminocarbonylation of Aliphatic Alkenes with N,N-Dimethylformamide as an in Situ Source of CO
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The palladium-catalyzed aminocarbonylation of aliphatic alkenes is presented for the first time without the need for external CO pressure. N,N-dimethylformamide (DMF) is used as an in situ source of both the required carbon monoxide and the amine substrate. The applied palladium catalytic system is well-known for a number of carbonylation reactions, including those with CO surrogates and tandem isomerizing carbonylations. The reaction pathway was investigated and proved to proceed by an acid-catalyzed DMF decomposition to CO and dimethyl amine with subsequent aminocarbonylation of the alkene. Pressure-versus-time curves gave more insight into the correlation between acid concentration and aminocarbonylation activity. Aliphatic alkenes (terminal and internal) are transformed, also in commercial glassware, into the corresponding linear N,N-dimethylamides with excellent selectivities. Hence, amide synthesis by aminocarbonylation moves closer to application in standard organic laboratories. Do-it-yourself CO production: The aminocarbonylation of alkenes for aliphatic amide synthesis is presented for the first time using N,N-dimethylamine as an in situ source of both, the required CO and dimethylamine. Excellent selectivities to the linear product are ensured by isomerizing carbonylation applying a [Pd]/1,2-DTBPMB system. 1,2-DTBPMB=1,2-bis((di-tert-butylphos- phino)methyl)benzene.
- Seidensticker, Thomas,Furst, Marc R. L.,Frauenlob, Robin,Vondran, Johanna,Paetzold, Eckhard,Kragl, Udo,Vorholt, Andreas J.
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p. 4085 - 4090
(2016/01/09)
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- Direct catalytic formation of primary and tertiary amides from non-activated carboxylic acids, employing carbamates as amine source
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The operationally simple titanium(IV)- or zirconium(IV)-catalyzed direct amidation of non-activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N-dimethyl-substituted amides in good to excellent yields. Copyright
- Tinnis, Fredrik,Lundberg, Helena,Adolfsson, Hans
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supporting information
p. 2531 - 2536
(2012/11/06)
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- Product selectivity in the electroreduction of thioesters
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The electroreduction of differently substituted aromatic and aliphatic thioesters (RCOSR′) led to regioselective reactions depending on the nature of the substituents. Thus, the cleavage between the carbonyl group and the SR′ group afforded α-diketones an
- We?wer,Olivero,Du?ach
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p. 1709 - 1714
(2007/10/03)
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- Vinyl-λ3-iodanes act as efficient sulfur atom acceptors: Vinylic SN2-based strategy for conversion of tertiary thioamides to amides
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Exposure of tertiary thioamides to (E)-1-hexenyl(phenyl)-λ3-iodane results in vinylic SN2 reaction to give the inverted (Z)-S-vinylthioimidonium salts, which under alkaline hydrolysis (Na2CO3 or K2CO
- Ochiai, Masahito,Yamamoto, Shinji
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p. 2802 - 2803
(2007/10/03)
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- Tetramethylammonium phenyltrialkylborates in the photoinduced electron transfer reaction with benzophenone. Generation of alkyl radicals and their addition to activated alkenes
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Photoinduced one electron oxidation of tetramethylammonium phenyltrialkylborates by the excited state of benzophenone in an acetonitrile/benzene solution containing an excess of activated alkene produces substantially more than one equivalent of the alkyl radicals. The corresponding adducts of alkyl radicals to the alkenes are produced in good yields. No phenyl radical adducts are observed.
- Polykarpov, Alexander Y.,Neckers, Douglas C.
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p. 5483 - 5486
(2007/10/02)
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- Synthesis of amides
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Alkyl amides have been synthesized from cyclic anhydrides, carboxyl acids and their esters by contacting them with an amine carbamic acid salt.
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