- Allylation of Alcohols and Carboxylic Acids with Allyl Acetate Catalyzed by [Ir(cod)2]+BF4- Complex
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A facile method for the synthesis of allyl alkyl ethers from alcohols with allyl acetate was developed by the use of [Ir(cod)2] +BF4- complex. For instance, the reaction of allyl acetate with n-octyl alcohol in the presence of a catalytic amount of [Ir(cod)2]+BF4- complex afforded allyl octyl ether in quantitative yield. Allyl carboxylates were also prepared by the exchange reaction between carboxylic acids and allyl acetate in good yields. The [Ir(cod)2]+BF4- complex catalyzed the reaction of alkyl and aromatic amines with allyl acetate to lead to the corresponding allylamines in fair to good yields.
- Nakagawa, Hideto,Hirabayashi, Tomotaka,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 3474 - 3477
(2007/10/03)
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- Solvent effects in deamination reactions
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Nitrous acid deaminations of (S)-2-butanamine, (2R,3S)-3-methyl-2-pentanamine (8), cyclopropananmine (17) and 4,4-dimethyl-2-adamantanamine (30) have been studied in water and in a series of carboxylic acids of decreasing polarity (acetic, 3,3-dimethylbutyric, 2-ethylhexanoic acid).The stereochemistry of aqueous deaminations varies from predominant inversion to predominant retention, depending upon the structure of the substrate (steric hindrance, neighbouring-group participation, etc.).In carboxylic acid media, alcohols arise with predominant retention, i.e. by front-side attack of the "internal" nucleophile (water).Inverting displacement of nitrogen by the "external" nucleophile (carboxylic acid/carboxylate) increases with decreasing polarity of the solvent.Even cyclopropanamine yields cyclopropyl esters (2-10percent) of inverted configuration, as shown with the aid of deuterium labels.Current mechanistic concepts are modified to account for these results.
- Banert, Klaus,Bunse, Michael,Engbert, Theodor,Gassen, Karl-Rudolf,Kurnianto, Apriana W.,Kirmse, Wolfgang
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p. 272 - 278
(2007/10/02)
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