- 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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- Stereodivergent trifluoromethylation of: N -sulfinylimines by fluoroform with either organic-superbase or organometallic-base
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Here we have successfully demonstrated the first stereodivergent direct nucleophilic trifluoromethylation of N-sulfinylimines using the potent greenhouse gas "HFC-23, fluoroform" with an organic-superbase or an organometallic-base in high yields and selectivity.
- Punna, Nagender,Saito, Takuya,Kosobokov, Mikhail,Tokunaga, Etsuko,Sumii, Yuji,Shibata, Norio
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supporting information
p. 4294 - 4297
(2018/05/07)
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- METHOD FOR PRODUCING OPTICALLY ACTIVE TRIFLUOROMETHYL GROUP-CONTAINING AMINO ACID DERIVATIVE
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PROBLEM TO BE SOLVED: To provide methods for producing optically active trifluoromethyl group-containing sulfinamide derivatives and optically active amino acids/hydrochlorides, using trifluoromethane as a generator of trifluoromethyl anions. SOLUTION: Th
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Paragraph 0123; 0124; 0125; 0126; 0127
(2019/02/28)
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- Palladium(II)-catalyzed enantioselective synthesis of α- (trifluoromethyl)arylmethylamines
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Trifluoromethylacetaldimines, generated in situ from the corresponding N,O-acetals, undergo 1,2-addition of arylboroxines under palladium(II) catalysis to generate a variety of α-(trifluoromethyl)arylmethylamines with good to high enantioselectivity (up to 97% ee). The pyridine-oxazolidine (PyOX) class of ligands was found to be particularly suitable for this transformation, which proceeds without exclusion of ambient air and moisture.
- Johnson, Thomas,Lautens, Mark
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supporting information
p. 4043 - 4045
(2013/09/12)
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- Diastereoselective addition of organomagnesium and organolithium reagents to chiral trifluoromethyl N-tert-butanesulfinyl hemiaminals
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The asymmetric synthesis of trifluoromethylated tertiary and secondary carbinamines (α,α-dibranched and α-branched amines) was achieved by reaction of alkyl, aryl and allyl organomagnesium or organolithium reagents to trifluoromethyl N-tert-butanesulfinyl
- Grellepois, Fabienne,Ben Jamaa, Abdelkhalek,Gassama, Abdoulaye
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supporting information
p. 6694 - 6701
(2013/11/06)
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- 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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- One-pot asymmetric synthesis of α-trifluoromethylated amines from α-trifluoromethyl ketones
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Diastereoselective reduction of (Rs)-N-tert-butanesulfinyl α-trifluoromethyl ketimines formed in situ from the corresponding α-trifluoromethyl ketones and N-tert-butanesulfinamide has been achieved, and either diastereomer of N-tert-butanesulfinyl α-trifl
- Xu, Jian,Liu, Zhen-Jiang,Yang, Xian-Jin,Wang, Li-Min,Chen, Guan-Long,Liu, Jin-Tao
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supporting information; experimental part
p. 8933 - 8937
(2011/01/04)
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- Enantiodivergent approach to trifluoromethylated amines: A concise route to both enantiomeric analogues of calcimimetic NPS R-568
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Reported herein is a straightforward and enantiodivergent synthesis of both enantiomers of trifluoromethylated analogues of calcimimetic NPS R-569 in a highly estereoselective manner. The synthesis features a diastereoselective synthesis of the N-(isopropylsulfinyl)imine unit by the "DAG methodology" and a diastereoselective addition of Ruppert Prakash's reagent to the imine as the key steps. No protecting groups were necessary, permitting an atom economic synthesis in only six steps. Further addition reactions of the CF3 anion to different N-(isopropylsulfinyl)imines were performed to demonstrate the suitability of the sulfinyl substituent to balance perfectly reactivity and diastereoselectivity.
- Fernandez, Inmaculada,Valdivia, Victoria,Alcudia, Ana,Chelouan, Ahmed,Khiar, Noureddine
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experimental part
p. 1502 - 1509
(2010/06/15)
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- Rhodium-catalyzed diastereoselective 1,2-addition of arylboronic acids to chiral trifluoroethyl imine
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Rhodium-catalyzed 1,2-addition of arylboronic acids 4a-j to chiral trifluoroethyl imine 3 afforded diastereomerically enriched sulfinamides 5a-j. The chiral auxiliary of the sulfinamide products was readily removed under acidic methanolysis to provide the corresponding trifluoroethylamine analogs 6a-j.
- Truong, Vouy Linh,Pfeiffer, Jennifer Y.
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scheme or table
p. 1633 - 1635
(2009/06/18)
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- Asymmetric syntheses of 1-Aryl-2,2,2-trifluoroethylamines via diastereoselective 1,2-addition of arylmetals to 2-Methyl-N-(2,2,2- trifluoroethylidene)propane-2-sulfinamide
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Condensation of N-tert-butanesulfinamide (S)-1 with trifluoroacetaldehyde hydrate 2a afforded 2-methyl-N-(2,2,2-trifluoroethylidene)propane-2-sulfinamide 3. Without isolation and purification, imine 3 was added to various aryllithium reagents to give high
- Truong, Vouy Linh,Menard, Madeleine S.,Dion, Isabelle
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p. 683 - 685
(2007/10/03)
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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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- THIADIAZOLES AS CXC- AND CC- CHEMOKINE RECEPTOR LIGANDS
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Disclosed are novel compounds of Formula (IA) and the pharmaceutically acceptable salts and solvates thereof. Examples of groups comprising Substituent A include heteroaryl, aryl, heterocycloalkyl, cycloalkyl, aryl, alkynyl, alkenyl, aminoalkyl, alkyl or amino. Examples of groups comprising Substituent B include aryl and heteroaryl. Also disclosed is a method of treating a chemokine mediated diseases, such as, cancer, angiogenisis, angiogenic ocular diseases, pulmonary diseases, multiple sclerosis, rheumatoid arthritis, osteoarthritis, stroke and ischemia reperfusion injury, pain (e.g., acute pain, acute and chronic inflammatory pain, and neuropathic pain) using a compound of Formula (IA).
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Page/Page column 156
(2010/02/12)
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- ISOTHIAZOLE DIOXIDES AS CXC- AND CC- CHEMOKINE RECEPTOR LIGANDS
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Disclosed are novel compounds of the formula (IA): and the pharmaceutically acceptable salts and solvates thereof. D and E are different groups wherein one is N and the other is CR50. Examples of groups comprising Substituent A include heteroaryl, aryl, heterocycloalkyl, cycloalkyl, aryl, alkynyl, alkenyl, aminoalkyl, alkyl or amino. Examples of groups comprising Substituent B include aryl and heteroaryl. Also disclosed is a method of treating a chemokine mediated diseases, such as, cancer, angiogenisis, angiogenic ocular diseases, pulmonary diseases, multiple sclerosis, rheumatoid arthritis, osteoarthritis, stroke and cardiac reperfusion injury, pain (e.g., acute pain, acute and chronic inflammatory pain, and neuropathic pain) using a compound of formula IA.
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Page/Page column 159
(2010/02/13)
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- THIADIAZOLEDIOXIDES AND THIADIAZOLEOXIDES AS CXC- AND CC-CHEMOKINE RECEPTOR LIGANDS
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Disclosed are novel compounds of the formula (IA) and the pharmaceutically acceptable salts and solvates thereof. Examples of groups comprising Substituent A include heteroaryl, aryl, heterocycloalkyl, cycloalkyl, aryl, alkynyl, alkenyl, aminoalkyl, alkyl or amino. Examples of groups comprising Substituent B include aryl and heteroaryl. Also disclosed is a method of treating a chemokine mediated diseases, such as, cancer, angiogenisis, angiogenic ocular diseases, pulmonary diseases, multiple sclerosis, rheumatoid arthritis, osteoarthritis, stroke and cardiac reperfusion injury, acute pain, acute and chronic inflammatory pain, and neuropathic pain using a compound of formula (IA).
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Page 184-185
(2008/06/13)
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- 3,4-Di-substituted cyclobutene-1,2-diones as CXC-chemokine receptor ligands
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There are disclosed compounds of the formula or a pharmaceutically acceptable salt or solvate thereof which are useful for the treatment of chemokine-mediated diseases such as acute and chronic inflammatory disorders and cancer.
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- 3,4-Di-substituted cyclobutene-1,2-diones as CXC-chemokine receptor ligands
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There are disclosed compounds of the formula or a pharmaceutically acceptable salt or solvate thereof which are useful for the treatment of chemokine-mediated diseases such as acute and chronic inflammatory disorders and cancer.
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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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