- Palladium-Catalyzed Double and Single Carbonylations of β-Amino Alcohols. Selective Synthesis of Morpholine-2,3-diones and Oxazolidin-2-ones and Applications for Synthesis of α-Oxo Carboxylic Acids
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Catalytic cross double carbonylation of secondary amines and alcohols proceeds in the presence of [PdCl2(MeCN)2] and CuI under carbon monoxide (80 atm) and oxygen (5 atm). Catalytic intramolecular double carbonylation of β-amino alcohols gives morpholine-2,3-diones, which are excellent protecting compounds of amino alcohols and important precursors for biologically active nitrogen compounds. In contrast, catalytic single carbonylation of β-amino alcohols under a mixture (1 : 1) of carbon monoxide and oxygen (1.0 atm) proceeds to give oxazolidin-2-ones selectively. The reaction can be explained by assuming a mechanism which includes intramolecular nucleophilic attack of the hydroxy group of (hydroxyethyl)aminocarbonyl ligands on the CO ligand of the carbamoylpalladium(II) complexes, followed by reductive elimination to give morpholine-2,3-diones. In contrast, direct nucleophilic attack of the hydroxy group to the carbamoyl group affords oxazolidin-2-ones. As a common intermediate for the double and single carbonylations, carbamoylpalladium(II) complex has been isolated by the reaction of [PdCl2(PMe3)2] with β-amino alcohol under CO. The present double carbonylation of amino alcohols provides a novel and convenient method for synthesis of α-oxo carboxylic acids. Thus, the morpholine-2,3-diones obtained undergo reaction with Grignard reagents chemoselectively at the ester positions to give 2-substituted 2-hydroxymorpholin-3-ones, which undergo acid hydrolysis to give α-oxo carboxylic acids.
- Imada, Yasushi,Mitsue, Yo,Ike, Kazuo,Washizuka, Ken-Ichi,Murahashi, Shun-Ichi
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p. 2079 - 2090
(2007/10/03)
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- REACTION OF ACTIVATED AZIRIDINES WITH AMINES
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The reactions of 1-alkoxycarbonylaziridines, 1-(phenylaminocarbonyl)aziridine, and 1-arylsulfonylaziridines with ammonia and amines were investigated.It was shown that the opening of the aziridine ring in a number of cases is accompanied by aminolysis of the alkoxycarbonyl group.The dependence of the ratio of ring opening and aminolysis products on the structure of the amines is discussed.
- Baranov, S. V.,Mochalin V. B.
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p. 951 - 953
(2007/10/02)
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