Mechanistic aspects of the synthesis of seven‐membered internal nitronates via stepwise [4 + 3] cycloaddition involving conjugated nitroalkenes: Molecular Electron Density Theory computational study

Kącka‐Zych, Agnieszka; Jasiński, Radomir

doi:10.1002/jcc.26885

Cited by 7 publications

(5 citation statements)

References 56 publications

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“…Within MCs, no new chemical bonds were formed. Similar-type intermediates have been identified recently regarding many bimolecular processes, such as 32CAs [32,[57][58][59], Diels-Alder reactions [54,60,61] and others [62][63][64]. Independent of the considered cycloaddition channel, the second reaction stage was a formation of the transition-state structure (TS) (Figure 2).…”

Section: Scheme 2 Competitive Paths For the Formation Of Regioisomeri...supporting

confidence: 65%

On the Question of the Formation of Nitro-Functionalized 2,4-Pyrazole Analogs on the Basis of Nitrylimine Molecular Systems and 3,3,3-Trichloro-1-Nitroprop-1-Ene

et al. 2022

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Experimental and theoretical studies on the reaction between (E)-3,3,3-trichloro-1-nitroprop-1-ene and N-(4-bromophenyl)-C-arylnitrylimine were performed. It was found that the title process unexpectedly led to 1-(4-bromophenyl)-3-phenyl-5-nitropyrazole instead of the expected Δ2-pyrazoline molecular system. This was the result of a unique CHCl3 elimination process. The observed mechanism of transformation was explained in the framework of the molecular electron density theory (MEDT). The theoretical results showed that both of the possible channels of [3 + 2] cycloaddition were favorable from a kinetic point of view, due to which the creation of 1-(4-bromophenyl)-3-aryl-4-tricholomethyl-5-nitro-Δ2-pyrazoline was more probable. On the other hand, according to the experimental data, the presented reactions occurred with full regioselectivity.

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Section: Scheme 2 Competitive Paths For the Formation Of Regioisomeri...supporting

confidence: 65%

On the Question of the Formation of Nitro-Functionalized 2,4-Pyrazole Analogs on the Basis of Nitrylimine Molecular Systems and 3,3,3-Trichloro-1-Nitroprop-1-Ene

et al. 2022

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“…For this purpose, the ωB97X-D/6-311G-(d) level of theory was applied. The similar approach we used previously for the discussion of mechanistic aspects of many bimolecular reactions, such as DA processes [ 45 ], [3 + 2] cycloadditions [ 46 ], [4 + 3] cycloaddition [ 47 ] and many other [ 35 , 48 ].…”

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confidence: 99%

Fully Selective Synthesis of Spirocyclic-1,2-oxazine N-Oxides via Non-Catalysed Hetero Diels-Alder Reactions with the Participation of Cyanofunctionalysed Conjugated Nitroalkenes

et al. 2023

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Hetero Diels-Alder (HDA) reactions with the participation of E-2-aryl-1-cyano-1-nitroethenes and methylenecyclopentane were evaluated on the basis of experimental as well as quantumchemical data. It was found that contrary to most known HDA reactions, title processes are realised under non-catalytic conditions and with full regiocontrol. The DFT study shows, without any doubt, the polar but single-step reaction mechanism. Deeper exploration using Bonding Evolution Theory (BET) techniques gives a clear image of the sequences of electron density reorganisation along the reaction coordinate. The first C4-C5 bond is created in phase VII by merging two monosynaptic basins, while the second O1-C6 bond is created in the last phase by a donation of the nonbonding electron density of O1 to C6. Based on the research, we can conclude that the analysed reaction proceeds according to a two-stage one-step mechanism.

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“…In this study, we carried out our investigation in relation to the 1 + 2a → 4a model process. A similar analysis was successfully performed for several different types of bimolecular processes [12][13][14].…”

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confidence: 99%

Full Regio- and Stereoselective Protocol for the Synthesis of New Nicotinoids via Cycloaddition Processes with the Participation of Trans-Substituted Nitroethenes: Comprehensive Experimental and MEDT Study

et al. 2023

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[3 + 2] Cycloaddition reactions with the participation of Z-C-(3-pyridyl)-N-methylnitrone and series of E-2-R-nitroethenes were both experimentally and theoretically explored in the framework of Molecular Electron Density Theory. It was found that all considered processes are realized under mild conditions and in full regio- and stereocontrol. The ELF analysis additionally showed that the studied reaction proceeds by a two-stage, one-step mechanism.

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Mechanistic aspects of the synthesis of seven‐membered internal nitronates via stepwise [4 + 3] cycloaddition involving conjugated nitroalkenes: Molecular Electron Density Theory computational study

Cited by 7 publications

References 56 publications

On the Question of the Formation of Nitro-Functionalized 2,4-Pyrazole Analogs on the Basis of Nitrylimine Molecular Systems and 3,3,3-Trichloro-1-Nitroprop-1-Ene

On the Question of the Formation of Nitro-Functionalized 2,4-Pyrazole Analogs on the Basis of Nitrylimine Molecular Systems and 3,3,3-Trichloro-1-Nitroprop-1-Ene

Fully Selective Synthesis of Spirocyclic-1,2-oxazine N-Oxides via Non-Catalysed Hetero Diels-Alder Reactions with the Participation of Cyanofunctionalysed Conjugated Nitroalkenes

Full Regio- and Stereoselective Protocol for the Synthesis of New Nicotinoids via Cycloaddition Processes with the Participation of Trans-Substituted Nitroethenes: Comprehensive Experimental and MEDT Study

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