- Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B12Derivative
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The B12derivative, heptamethyl cobyrinate, -mediated electrochemical synthesis of cyanoformamides has been developed. Aerobic oxygenation of the carbon-centered radical initiatedin situgeneration of the reactive acyl chloride intermediate, whic
- Moniruzzaman, Mohammad,Yano, Yoshio,Ono, Toshikazu,Shimakoshi, Hisashi,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio
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p. 16134 - 16143
(2021/07/19)
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- The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles
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A mild and efficient method for the synthesis of cyanoformamides from N,N-disubstituted aminomalononitriles with CsF as the promoter has been developed. This method features a wide substrate scope and high reaction efficiency, and will facilitate corresponding cyanoformamide-based biological studies and synthetic methodology development.
- Lei, Lin-Sheng,Xue, Cao-Gen,Xu, Xue-Tao,Jin, Da-Ping,Wang, Shao-Hua,Bao, Wen,Liang, Huan,Zhang, Kun,Asiri, Abdullah M.
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p. 3723 - 3726
(2019/04/17)
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- Solvent-Free Synthesis of Cyanoformamides from Carbamoyl Imidazoles
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A straightforward and solvent-free synthesis of various secondary and tertiary cyanoformamides from carbamoyl imidazoles and TMSCN has been developed. Both cyclic and acyclic carbamoyl imidazoles react smoothly to form the relevant cyanoformamides in excellent yields, often within minutes.
- Nugent, Jeremy,Campbell, Sarah G.,Vo, Yen,Schwartz, Brett D.
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p. 5110 - 5118
(2017/09/23)
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- Transition-Metal-Free Conversion of Trifluoropropanamides into Cyanoformamides through C-CF3 Bond Cleavage and Nitrogenation
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A new transition-metal-free transformation of trifluoropropanamides into cyanoformamides through a sequence of C-CF3 bond cleavage and nitrogenation using tert-butyl nitrite as the nitrogen source is described. The method features direct detrifluoromethylation, broad substrate scopes, and excellent selectivity control, representing a new shortcut for constructing the nitrile group involving C-CF3 σ-bond cleavage.
- Wang, Fang,Zhang, Tao,Tu, Hai-Yong,Zhang, Xing-Guo
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p. 5475 - 5480
(2017/05/24)
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- Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp2 C-H and sp3 C-H bonds
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The synthesis of a variety of 2-oxindoles bearing an all-carbon quaternary center at the pseudo benzylic position has been achieved via a 'transition-metal-free' intramolecular dehydrogenative coupling (IDC). The construction of 2-oxindole moieties was carried out through formation of carbon-carbon bonds using KOt-Bu-catalyzed one pot C-alkylation of β-N-arylamido esters with alkyl halides followed by a dehydrogenative coupling. Experimental evidences indicated toward a radical-mediated path for this reaction.
- Kumar, Nivesh,Ghosh, Santanu,Bhunia, Subhajit,Bisai, Alakesh
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supporting information
p. 1153 - 1169
(2016/07/06)
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- PhI(OAc)2-promoted metal-free oxidation of 2-oxoaldehydes: a facile one-pot synthesis of cyanoformamides
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A novel, efficient and environmental method for the conversion of 2-oxoaldehydes into cyanoformamides with iodosobenzene diacetate as oxidant has been developed. The reactions proceeded smoothly at room temperature under metal-free conditions and generate
- Zhan, Zhen,Cheng, Xu,Zheng, Yang,Ma, Xiaojun,Wang, Xiaoyu,Hai, Li,Wu, Yong
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p. 82800 - 82803
(2015/10/19)
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- Tert-Butyl Hydroperoxide and Tetrabutylammonium Iodide-Promoted Free Radical Cyclization of α-Imino-N-arylamides and α-Azido-N-arylamides
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The oxidizing system of tert-butyl hydroperoxide (TBHP) and tetrabutylammonium iodide (TBAI) is capable of generating α-(arylaminocarbonyl)iminyl radicals from ethyl 2-(N-arylcarbamoyl)-2-iminoacetates. These iminyl radicals preferably undergo intramolecular ipso attack on the benzene ring to give azaspirocyclohexadienyl radicals, which are readily captured by molecular oxygen under an oxygen atmosphere to yield azaspirocyclohexadienones. In the absence of oxygen, the reaction affords quinoxalin-2-one products. This oxidizing system is also effective to convert α-aryl-α-azido-N-arylamides to the corresponding iminyl radicals under basic conditions (sodium tert-butoxide, t-BuONa), and the subsequent cyclization of these iminyl radicals results in the formation of azaspirocyclohexadienone products in high yields under an oxygen atmosphere. Plausible mechanisms are proposed to rationalize the experimental results, and factors influencing the reactions are discussed.
- Li, Dianjun,Yang, Tonghao,Su, Hailin,Yu, Wei
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p. 2529 - 2539
(2015/08/18)
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- POCl3-mediated reaction of 1-Acyl-1-carbamoyl Oximes: A new entry to cyanoformamides
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A facile and efficient one-pot synthesis of cyanoformamides was developed from readily available 1-acyl-1-carbamoyl oximes mediated by phosphoryltrichloride (POCl3) under mild conditions in good to high yields.
- Yang, Jiming,Xiang, Dexuan,Zhang, Rui,Zhang, Ning,Liang, Yongjiu,Dong, Dewen
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supporting information
p. 809 - 811
(2015/03/18)
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- Unexpected zirconium-mediated multicomponent reactions of conjugated 1,3-butadiynes and monoynes with acyl cyanide derivatives
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Going ber(zirc): Zirconium-butadiyne complexes react with acyl cyanide derivatives through diverse reaction pathways. The complexes react with two molecules of carbamoyl cyanide to form 1,4-benzodiazepin-2-one-derivatives containing azazirconacycles. Reac
- Yu, Shasha,You, Xu,Liu, Yuanhong
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supporting information
p. 13936 - 13940
(2013/01/15)
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- Copper-catalyzed synthesis of azaspirocyclohexadienones from ∝-azido- N -arylamides under an oxygen atmosphere
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A copper-catalyzed reaction of ∝-azido-N-arylamides was found to proceed under an oxygen atmosphere to afford azaspirocyclohexadienones. The present transformation is carried out by a sequence of denitrogenative formation of iminyl copper species from ∝-azido-N-arylamides and their imino-cupration with an intramolecular benzene ring on the amido nitrogen followed by consecutive formation of C-O bonds. The preliminary investigation revealed that molecular oxygen is a prerequisite for achieving the present catalytic cyclization and that one of the oxygen atoms of O2 was found to be incorporated into the cyclohexadienone moiety.
- Chiba, Shunsuke,Zhang, Line,Lee, Jian-Yuan
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supporting information; experimental part
p. 7266 - 7267
(2010/08/05)
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- Iminyl radicals from α-azido o-iodoanilides via 1,5-H transfer reactions of aryl radicals: New transformation of α-azido acids to decarboxylated nitriles
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(Chemical Equation Presented) The radical reaction of tributyltin hydride with o-iodo-N-methylanilides derived from α-azido acids provides an excellent access to α-(aminocarbonyl)iminyl radicals through 1,5-hydrogen transfer reaction of initially formed aryl radicals followed by β-elimination of dinitrogen from ensuing α-azido-α- (aminocarbonyl)alkyl radicals. The outcoming iminyls display a peculiar tendency to form corresponding nitriles by β-elimination of aminocarbonyl radicals.
- Bencivenni, Giorgio,Lanza, Tommaso,Leardini, Rino,Minozzi, Matteo,Nanni, Daniele,Spagnolo, Piero,Zanardi, Giuseppe
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p. 4721 - 4724
(2008/09/21)
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- 2-(N-Methylanilino)-2-phenylsulfanylacetonitrile, A Reagent Tested for Electrophilic, Nucleophilic, and Radical Reactions
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2-(N-Methylanilino)-2-phenylsulfanylacetonitrile 1 has been readily prepared from 2-(N-methylanilino)acetonitrile and diphenyl disulfide.Alkylation of the anion of 1 with halogenoalkanes resulted in concurrent elimination of benzenethiol to give conjugated α-aminoalkenenitriles of 2E-configuration.Autoxidation of 1 in the presence of alkoxide ions afforded alkyl N-methyl-N-phenylcarbamates.Nucleophilic substitution of 1 with Grignard reagent or appropriate silyl compounds were promoted by CuI or Lewis acids to give varied α-amino nitriles.The 4-oxo-2-aminonitriles 9 obtained by condensation of 1 and titanium enolates can be considered as derivatives of 1,3-dicarbonyl compounds with the aldehyde group being activated to give an amino nitrile umpolung.When 1 was treated with tributylstannane, the corresponding amino nitrile α-radical was formed and the self-coupling product was isolated.
- Chen, Chih-Cheng,Chen, Same-Ting,Chuang, Tsung-Hsun,Fang, Jim-Min
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p. 2217 - 2222
(2007/10/02)
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- Solution and Solid-State Photochemistry of 2-Anilino-5-phenyl-2,4-pentadienenitriles
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2-(N-Methylanilino)-5-phenyl-2,4-pentadienenitrile (3) undergoes either isomerization or oxidative cleavage at the 2,3-double bond upon irradiation in solution, whereas it dimerizes in a regiospecific manner to give the cycloaddition product 12 upon irradiation in the solid state.From the fluorescence spectra and semiempirical calculations, the excited state of 3 is proposed to be a twist intramolecular charge transfer species.The X-ray analysis indicates that molecules of 3b orient appropriately with a reasonable distance for the cycloaddition in the solid state.The distance between C2 and C3' is 525 pm, the longest distance known in solid-state cycloadditions. 2-(N-Methyl-p-bromoanilino)-5-phenyl-2,4-pentadienenitrile (4) shows behavior similar to that of 3 in the solution and solid-state photochemistry, whereas analogs 7-10 having nitro substituents on the 5-phenyl rings do not dimerize upon irradiation in the solid state.Semiempirical calculation of the electronic structures is used to interprete the discrepancy of reactivity.
- Liang, Yah-Long,Fang, Jim-Min,Chow, Tahsin,Ho, Tong-Ing,Lee, Chi-Rung,Wang, Yu
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p. 5742 - 5747
(2007/10/02)
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