- Iron porphyrin-catalyzedN-trifluoroethylation of anilines with 2,2,2-trifluoroethylamine hydrochloride in aqueous solution
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An iron porphyrin-catalyzedN-trifluoroethylation of anilines has been developed with 2,2,2-trifluoroethylamine hydrochloride as the fluorine source. This one-pot N-H insertion reaction is conductedviacascade diazotization/N-trifluoroethylation reactions.
- Guo, Cancheng,Guo, Yongjia,Liu, Qiang,Ren, Shuang,Xu, Guiming
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p. 20322 - 20325
(2021/06/26)
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- NaOTs-promoted transition metal-free C-N bond cleavage to form C-X (X = N, O, S) bonds
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Multifunctional transformation of amide C-N bond cleavage is reported. The protocol applies to benzamide, thioamide, alcohols, and mercaptan under similar reaction conditions catalyzed by NaOTs. It is noteworthy that NaOTs can not only be recycled and reused for up to three cycles without significant loss in catalytic activity, but also catalyze gram-grade reactions. This study provides a novel solution with mild conditions and a simple procedure for transformation of multiple amides.
- Chen, Wei,Liu, Sicheng,Liu, Tingting,Majeed, Irfan,Ye, Xiaojing,Zeng, Zhuo,Zhang, Yuqi,Zhu, Yulin
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supporting information
p. 8566 - 8571
(2021/10/20)
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- Direct N-Alkylation/Fluoroalkylation of Amines Using Carboxylic Acids via Transition-Metal-Free Catalysis
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A scalable protocol of direct N-mono/di-alkyl/fluoroalkylation of primary/secondary amines has been constructed with various carboxylic acids as coupling agents under the catalysis of a simple air-tolerant inorganic salt, K3PO4. Advantageous features include 100 examples, 10 drugs and drug-like amines, fluorinated complex tertiary amines, gram-scale synthesis and isotope-labelling amine, thus demonstrating the potential applicability in industry of this methodology. The involvement of relatively less reactive silicon-hydride compared with the traditional reactive metal-hydride or boron-hydride species required to reduce the amide intermediates presumably contributes to the remarkable functional group compatibility. (Figure presented.).
- Lu, Chunlei,Qiu, Zetian,Xuan, Maojie,Huang, Yan,Lou, Yongjia,Zhu, Yiling,Shen, Hao,Lin, Bo-Lin
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supporting information
p. 4151 - 4158
(2020/08/21)
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- Method of catalyzing trifluoro-ethylation of aromatic primary amine by ferriporphyrin
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The invention provides a method of catalyzing trifluoro-ethylation of aromatic primary amine by ferriporphyrin. The method comprises the following steps: adding trifluoroethylamine salt and nitrite toa diazo-reaction first and then adding aromatic primary
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Page/Page column 16
(2019/01/08)
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- Cu-Catalyzed/mediated synthesis of N-fluoroalkylanilines from arylboronic acids: fluorine effect on the reactivity of fluoroalkylamines
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An oxidative coupling reaction of fluoroalkylamines with arylboronic acids has been achieved for the first time. Fluorine has profound influence on the reactivity and fluoroalkylated amines have the following reactivity trend: difluoroethylamine > trifluo
- Wang, Hui,Tu, Yuan-Hong,Liu, De-Yong,Hu, Xiang-Guo
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supporting information
p. 6634 - 6637
(2018/09/29)
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- PREPARATION OF SECONDARY AMINES WITH ELECTROPHILIC N-LINCHPIN REAGENTS
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In one aspect, the present disclosure provides methods of preparing a secondary amine. In some embodiments, the secondary amine comprises two different groups or two identifical groups. Also provided herein are compositions for use in the preparation of the secondary amine.
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Page/Page column 101-102
(2018/12/13)
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- Transition metal-free: N -fluoroalkylation of amines using cyanurate activated fluoroalcohols
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A novel and highly efficient method for N-fluoroalkylation of amines using 2,4,6-tris(fluoroalkoxy)-1,3,5-triazines was developed. This simple approach allowed the N-fluoroalkylation of amines under fast, mild and efficient reaction conditions, without using a transition metal as a catalyst.
- Haghighi, Fatemeh,Panahi, Farhad,Golbon Haghighi, Mohsen,Khalafi-Nezhad, Ali
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supporting information
p. 12650 - 12653
(2017/12/02)
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- Silver(I)-Catalyzed N-Trifluoroethylation of Anilines and O-Trifluoroethylation of Amides with 2,2,2-Trifluorodiazoethane
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A straightforward N-trifluoroethylation of anilines has been developed based on silver-catalyzed N£H insertions with 2,2,2-trifluorodiazoethane (CF3CHN2). Mechanistically, the reaction is proposed to involve migratory insertion of a silver carbene as the key step. In contrast, when amides are employed as the substrates under similar reaction conditions, O-trifluoroethylation occurs to afford trifluoroethyl imidates.
- Luo, Haiqing,Wu, Guojiao,Zhang, Yan,Wang, Jianbo
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supporting information
p. 14503 - 14507
(2016/01/25)
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- Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids
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A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.
- Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
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p. 9042 - 9046
(2015/08/03)
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- Direct catalytic N-alkylation of amines with carboxylic acids
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A straightforward process for the N-alkylation of amines has been developed applying readily available carboxylic acids and silanes as the hydride source. Complementary to known reductive aminations, effective C-N bond construction proceeds under mild conditions and allows obtaining a broad range of alkylated secondary and tertiary amines, including fluoroalkyl-substituted anilines as well as the bioactive compound Cinacalcet HCl.
- Sorribes, Iván,Junge, Kathrin,Beller, Matthias
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p. 14314 - 14319
(2014/12/10)
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- NOVEL COMPOUNDS
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The present invention relates to new CGRP-antagonists of general formula I wherein U, V, X, Y, R1, R2, R3 and R4 are defined as in the description, the tautomers, the isomers, the diastereomers, the enantiomers, the hydrates, the mixtures thereof and the salts thereof and the hydrates of the salts, particularly the physiologically acceptable salts thereof with inorganic or organic acids or bases, medicaments containing these compounds, their use and processes for preparing them.
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Page/Page column 40-41
(2011/02/18)
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- Trifluoroacetaldehyde: A useful industrial bulk material for the synthesis of trifluoromethylated amino compounds
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The synthesis of various trifluoromethylated amino compounds was studied using trifluoroacetaldehyde, an industrial bulk material, as a starting compound. One general application of trifluoroacetaldehyde is the preparation of trifluoroethylamino derivatives via reductive amination reaction. This synthesis includes the formation of the corresponding N,O-acetal intermediates followed by their reduction using NaBH4 or 2-picoline borane complex, affording the target trifluoroethylamino compounds in moderate to good yields (47-87%). Another general application of trifluoroacetaldehyde is the synthesis of chiral α-substituted trifluoroethylamino compounds. In this synthesis, trifluoroacetaldehyde was first converted into the chiral trifluoromethyl tert-butyl sulfinimine, which was subjected to 1,2-nucleophilic addition reactions across its C{double bond, long}N double bond. The addition of phenyllithium afforded α-(phenyl)trifluoroethylamino derivative in 83% yield and with 96% de. Allylation and Reformatsky reactions produced the corresponding α-substituted trifluoroethylamino derivatives in 82 and 58% yields and with 90 and 91% de, respectively.
- Mimura, Hideyuki,Kawada, Kosuke,Yamashita, Tetsuya,Sakamoto, Takeshi,Kikugawa, Yasuo
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experimental part
p. 477 - 486
(2010/05/02)
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- Electrolytic Reactions of Fluoroorganic Compounds. 14. Regioselective Anodic Methoxylation of N-(Fluoroethyl)amines. Preparation of Highly Useful Fluoroalkylated Building Blocks
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Anodic methoxylation of various types of N-(fluoroethyl)amines, ArRNCH2Rf (Rf = CF3, CHF2, CH2F, etc.) has been systematically studied and it was found that a methoxy group was exclusively or preferentially introduced into the position α to the fluoromethyl (Rf) group, depending on the Rf and R groups.The effect of the Rf group on the promotion of the anodic α-methoxylation decreased in the order CF3, CHF2, and CH2F.This remarkable promotion effect and unique regioselectivity can be explained mainly in terms of the α-CH kinetic acidities of the cation radicals formed by one-electron oxidation of the amines.The α-methoxylated products are highly useful precursors for the construction of carbon-carbon bonds α to the trifluoromethyl and difluoromethyl groups, which is difficult by other methods.
- Fuchigami, Toshio,Ichikawa,, Shinji
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p. 607 - 615
(2007/10/02)
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- Fluoroalkylaryliodonuim compounds
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Fluoroalkylaryliodonium compounds having the formula (I): STR1 wherein AR, A and Rf are as defined above, are disclosed. The fluoroalkylaryliodonium compounds of the present invention are useful as intermediates for producing N-fluoroalkylanilines or deri
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- 1,1-dihydroperfluoroalkylations of nucleophiles with (1,1-dihydroperfluoroalkyl)phenyliodonium triflates
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It was demonstrated that (1,1-dihydroperfluoroalkyl)phenyliodonium triflates (FMITS) served as very useful sources of 1,1- dihydroperfluoroalkyl cations. With a variety of nucleophiles, the corresponding fluoroalkyl derivatives were obtained.
- Umemoto, Teruo,Gotoh, Yoshihiko
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p. 231 - 236
(2007/10/07)
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- Light-induced Reactions of 2-(N-Alkyl-N-arylamino)cyclohexanones and Related Amino-cycloalkanones: Formation of 7-Azabicyclooctan-1-ols
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On irradiation, 2-(N-alkyl-N-arylamino)cyclohexanones (aryl = Ph; alkyl = Me, benzyl, allyl, Et, CH2CH2Ph, or CH2CF3; or aryl = p-tolyl; alkyl = Me) (10) or (20), 4,4-dimethyl-2-(N-methylanilino)-cyclohexanone (24), and 2-(N-methylanilino)-5α-cholestan-3-one (26) underwent type-II cyclisation to afford azetidinol (7-azabicyclooctan-1-ol) derivatives.In general, fission to give the corresponding N-alkyl-N-arylamine and ketone was a minor photoreaction.When the alkyl group of the 2-(N-alkylanilino)cyclohexanone had the structure -CH(R)CH2R', a double 1,5-hydrogen transfer occurred leading to a low yield of a 2-anilinocyclohexanol (31a).Photolysis of 2-anilinocyclohexanone (32a) gave a little of the direct-fission product aniline (17a), and the alkylamino-ketones 2-(NN-diethylamino)- (32b) and 2-(N-pyrrolidino)-cyclohexanone (32c) underwent no significant photoreaction in methanol.The isolation of indan-1-one and N-trideuteriomethylaniline on irradiation of 2-(N-trideuteriomethylanilino)-indan-1-one (33b) in diethyl ether indicated that the photoreaction was a direct Cα-N bond fission and not a type-II fission.
- El-Hamamy, Ahmad A.,Hill, John,Townend, John
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p. 573 - 580
(2007/10/02)
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