- Thermocontrolled benzylimine-benzaldimine rearrangement over Nafion-H catalysts for efficient entry into α-trifluoromethylbenzylamines
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Nafion-H and Nafion SAC-13 are efficient solid Br?nsted acid catalysts for the preparation of trifluoromethyl ketimines from benzylamines and trifluoromethylated ketones in high yields. A finely tuned benzylimine- benzaldimine rearrangement by facile 1,3-hydrogen shift has been achieved for the formation of fluorinated benzaldimines in high yields by careful optimization of reaction conditions including attempts under microwave conditions and a flow system. These α-trifluoromethylated benzaldimines are efficient precursors for pharmaceutically important α- trifluoromethylated benzylamines, accessed through their direct acid hydrolysis.
- Prakash, G.K. Surya,Glinton, Kevin E.,Panja, Chiradeep,Gurung, Laxman,Battamack, Patrice T.,T?r?k, Béla,Mathew, Thomas,Olah, George A.
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experimental part
p. 607 - 611
(2012/02/13)
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- Thermal 1,3-proton shift reaction and its application for operationally convenient and improved synthesis of α-(trifluoromethyl)benzylamine
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This paper describes a synthesis of α-(trifluoromethyl)benzylamine via a novel base-free biomimetic reductive amination of α,α,α-trifluoroacetophenone with benzylamine. When the corresponding imine, derived from α,α,α-trifluoroacetophenone and benzylamine
- Yasumoto, Manabu,Ueki, Hisanori,Soloshonok, Vadim A.
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p. 736 - 739
(2008/03/12)
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- Synthesis of alpha fluoroalkyl amines
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This invention describes the reaction of an alpha fluoroalkyl ketone with a bis(trialkylsilyl)amide to give a stable N-trialkylsilyl imine. Treatment of the N-trialkylsilyl imine with an alcohol leads to solvolysis of the trialkylsilyl group and yields a
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Page/Page column 3
(2008/06/13)
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- Unprecedented catalytic asymmetric reduction of N-H imines
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(Chemical Equation Presented) Addition of lithium bis(trimethylsilyl)amide to perfluorinated ketones 1a-j affords (E)-N-TMS-ketimines 2a-j that are reduced in situ to afford racemic perfluoromethylated amine hydrochloride salts 3a-j in 54-97% yields. Solv
- Gosselin, Francis,O'Shea, Paul D.,Roy, Stephanie,Reamer, Robert A.,Chen, Cheng-Yi,Volante, Ralph P.
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p. 355 - 358
(2007/10/03)
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- Biomimetic reductive amination of fluoro aldehydes and ketones via [1,3]-proton shift reaction. Scope and limitations
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A systematic study of azomethine-azomethine isomerizations of the N-benzylimines 2, derived from fluorinated aldehydes or ketones and benzylamine, has been made. The results reveal that, in sharp contrast to hydrocarbon analogs, fluorinated imines of 2 in triethylamine solution undergo isomerizations to give the corresponding N-benzylidene derivatives 5 (for 5/2 K > 32) in good isolated yields. The rates of the isomerizations depend on the starting imine structures and increase in the following order: aryl perfluoroalkyl ketimine 2m, per(poly)fluoroalkyl aldimine 2a,d-g, perfluoroaryl aldimine 2h, alkyl perfluoroalkyl ketimine 2i,j. The presence of chlorine or bromine atoms in the α-position to the C=N double bond of the starting imine favors a dehydrohalogenation reaction, giving rise to unsaturated products 6-9. The azomethine-azomethine isomerization was studied and proven to proceed essentially (>98%) intramolecularly with isotope exchange experiments. High chemical yields, the simplicity of the experimental procedure, and the low cost of all reagents employed make this biomimetic transamination of fluorocarbonyl compounds a practical method for preparing fluorine-containing amines of biological interest.
- Ono, Taizo,Kukhar, Valery P.,Soloshonok, Vadim A.
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p. 6563 - 6569
(2007/10/03)
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- A practical route to fluoroalkyl- and fluoroarylamines by base-catalyzed [1,3]-proton shift reaction
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The base-catalyzed [1,3]-proton shift reaction is shown to be an efficient general approach to fluoroalkyl and fluoroaryl amines starting from appropriate carbonyl compounds and benzylamine.
- Soloshonok,Soloshonok, Vadim A.,Kirilenko,Kirilenko, Alexander G.,Kukhar,Kukhar, Valery P.,Resnati,Resnati, Giuseppe
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p. 3119 - 3122
(2007/10/02)
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- AZOMETHINE-AZOMETHINE ISOMERIZATION IN THE SERIES OF FLUORINE-CONTAINING N-BENZYLIMINES
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The reaction of N-benzyltriphenylphosphine imide with fluorine-containing carbonyl compounds leads to the corresponding N-benzylimines.The latter readily isomerize under the influence of bases to N-benzylidene derivatives.
- Soloshonok, V. A.,Gerus, I. I.,Yagupol'skii, Yu. L.,Kukhar', V. G.
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p. 895 - 899
(2007/10/02)
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