- Single-Step Approach toward Nitrones via Pyridinium Ylides: The DMAP-Catalyzed Reaction of Benzyl Halides with Nitrosoarenes
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A single-step approach is reported for the preparation of nitrones from benzyl halides and nitrosoarenes via pyridinium ylides, utilizing 4-dimethylaminopyridine (DMAP) catalyst and mild reaction conditions (Li2CO3, dimethylacetamide, and room temperature). The reaction provides both keto-and aldonitrones in high yields with a wide scope for benzyl halides and nitrosoarenes. In the same reaction system, 2-methyl-2-nitrosopropane, which does not have an aryl group, also affords the corresponding N-tert-butyl nitrones from primary benzyl bromides that have an electron-withdrawing group. As an application of the reaction, methyl 2-bromo-2-phenylacetate was used to prepare the corresponding isoxazolidine by a sequential one-pot synthesis.
- Jung, Yeonghun,Hong, Jee Eun,Kwak, Jae-Hwan,Park, Yohan
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p. 6343 - 6350
(2021/05/29)
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- A Protocol to Transform Sulfones into Nitrones and Aldehydes
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A simple method to transform sulfones into nitrones and therefore into the corresponding carbonyl derivatives has been developed. Some examples demonstrate that it is a new reliable and versatile reaction in the toolbox of sulfones that has great synthetic potential. NMR and computational studies were used to elucidate the mechanism.
- Rodrigo, Eduardo,Alonso, Inés,Cid, M. Belén
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supporting information
(2018/09/27)
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- A Protocol to Transform Sulfones into Nitrones and Aldehydes
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A simple method to transform sulfones into nitrones and therefore into the corresponding carbonyl derivatives has been developed. Some examples demonstrate that it is a new reliable and versatile reaction in the toolbox of sulfones that has great synthetic potential. NMR and computational studies were used to elucidate the mechanism.
- Rodrigo, Eduardo,Alonso, Inés,Cid, M. Belén
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supporting information
p. 5789 - 5793
(2018/09/29)
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- Coupling of N -Nosylhydrazones with Nitrosoarenes: Transition-Metal-Free Approach to (Z)- N -Arylnitrones
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An efficient and transition-metal-free protocol for the synthesis of (Z)- N -arylnitrones from the direct coupling of N -nosylhydrazones with nitrosoarenes under mild conditions is described. The protocol is compatible with a wide range of functional groups placed on both the reagents and provided the corresponding nitrones in good to excellent yields by simple recrystallization process. The use of these 1,3-dipoles for the synthesis of substituted indoles is elaborated for 2,3-diphenyl-1 H -indole.
- Liu, Tingting,Liu, Zhaohong,Liu, Zhenhua,Hu, Donghua,Wang, Yeming
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p. 1728 - 1736
(2018/02/14)
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- Cycloaddition of Fluorenone N-Aryl Nitrones with Methylenecyclopropanes and Sequential 1,3-Rearrangement: An Entry to Synthesis of Spirofluorenylpiperidin-4-ones
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A facile synthesis of various spirofluorenylpiperidin-4-ones has been achieved in good yields from fluorenone N-aryl nitrones and methylenecyclopropanes. This method involved an initial cycloaddition to form a 5-spirocyclopropane-isoxazoline, which underwent a highly selective 1,3-rearrangement to give the desired product. The stereochemistry of the spirofluorenylpiperidin-4-one could be controlled by the cycloaddition and sequential rearrangement strategy. Furthermore, the spirofluorenylpiperidin-4-ones could be not only prepared in one-pot procedure but also converted to useful scaffolds by reduction or oxidation conditions.
- Ma, Xiao-Pan,Zhu, Jie-Feng,Wu, Si-Yi,Chen, Chun-Hua,Zou, Ning,Liang, Cui,Su, Gui-Fa,Mo, Dong-Liang
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p. 502 - 511
(2017/04/26)
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- Metal-free synthesis of highly substituted quinolines under mild conditions Dedicated to Professor Jonathan S. Lindsey on his sixtieth birthday
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Starting from easily accessible nitrones and acetylenes, a simple, metal free synthesis of substituted quinolines under mild conditions with high atom efficiency has been developed. Our method is flexible enough to introduce substituents regiospecifically
- Natarajan, Rakesh,Unnikrishnan, Peruparambil A.,Radhamani, Sandhya,Rappai, John P.,Prathapan, Sreedharan
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p. 2981 - 2984
(2016/07/06)
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- Electrochemically Induced Chain Reactions: The Electrochemical Behavior of Nitrosobenzene in the Presence of Proton Donors in Tetrahydrofuran
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The electrochemical reduction of nitrosobenzene in tetrahydrofuran with tetrabutylammonium hexafluorophosphate as the supporting electrolyte and in the presence of fluorene or indene at room temperature gives a mixture of an anil (1 or 3), a nitrone (2 or 4), and azoxybenzene and requires only a catalytic amount of electricity.Lowering the temperature and/or increasing the proportion of proton donor favors the formation of the anil at the expense of the nitrone and azoxybenzene: a 97percent yield of anil 1 was obtained from an electrolysis carried out at -30 deg C using 5 equiv of fluorene.The possible steps of the chain reactions involved are discussed on the basis of electrochemical and chemical data and digital simulation.With phenylacetylene as the proton donor, there is no reaction between nitrosobenzene and phenylacetylene and azoxybenzene is the main product formed.
- Mugnier, Yves,Gard, Jean-Christophe,Huang, Youqin,Couture, Yvon,Lasia, Andrzej,Lessard, Jean
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p. 5329 - 5334
(2007/10/02)
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- Imines and Derivatives. Part 24. Nitrone Synthesis by Imine Oxidation using either a Peroxyacid or Dimethyldioxirane
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The oxidation of N-alkyl imines by m-chloroperoxybenzoic acid to yield nitrones was facilitated by (i) the presence of C-aryl substituents, (ii) steric inhibition of attack at the imino C-atom, (iii) electron donating para-substituents on the C-aryl substituent, (iv) non-hydroxylic solvents, (v) optimal conjugation between C-aryl substituents and the imino group, and (vi) less bulky N-alkyl groups. The oxidation of N-alkyl imines by dimethyldioxirane (DMD) in dichloromethane-acetone solution yielded nitrones without evidence of oxaziridine formation.The yields of isolated nitrones were higher for C,C-diaryl imines and for imines bearing less bulky N-alkyl substituents.N-H substituted ketimines were found to yield oximes after reaction with dimethyldioxirane.
- Boyd, Derek R.,Coulter, Peter B.,McGuckin, M. Rosaleen,Sharma, Narain D.,Jennings, W. Brian,Wilson, Valerie E.
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p. 301 - 306
(2007/10/02)
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- CYCLO-ADDITION REACTIONS OF THIOFLUORENONE WITH NITRONES
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Thiofluorenone reacts with C-phenyl-N-methylnitrone to give, initially, a 1,2,5-oxathiazolidine.Spontaneous loss of sulphur monoxide then produces a dipolar species which reacts with a second molecule of thiofluorenone to give a 1,2-thiazolidine.This thiazolidine partially isomerizes to a 1,3-thiazolidine on heating.The corresponding 1,2-thiazolidine 1-oxide similarly undergoes a cycloreversion-recyclization reaction to the isomeric 1,3-thiazolidine 1-oxide.The reaction of thiofluorenone with C-phenyl-N-phenylnitrone gives a 1,2-thiazetidine 1-oxide, a benzothiazine S-oxide, and a thiazolidine.The formation of the first two products can be explained by involving a rearrangement of the primary 1:1 adduct; the last product may derive from the same adduct by loss of sulphur monoxide followed by a reaction with a second molecule of thione.
- Mazzanti, Germana,Maccagnani, Gaetano,Bonini, Bianca F.,Pedrini, Paola,Zwanenburg, Binne
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p. 163 - 166
(2007/10/02)
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