Regiospecific formation of the nitromethyl-substituted 3-phenyl-4,5-dihydroisoxazole via [3 + 2] cycloaddition

Mirosław, Barbara; Babyuk, Dmytro; Łapczuk-Krygier, Agnieszka; Kącka‐Zych, Agnieszka; Demchuk, Oleg M.; Jasiński, Radomir

doi:10.1007/s00706-018-2227-6

Cited by 19 publications

(11 citation statements)

References 43 publications

(35 reference statements)

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“…A similar approach, entering in Molecular Electron Density Theory (MEDT) [ 27 ], to elucidate the molecular mechanism has been used successfully in various types of reactions. The used computational method has been shown to give results that are in complete agreement with experimental outcomes of previous reactions [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ].…”

Section: Computational Detailssupporting

confidence: 73%

The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

Kącka‐Zych

2021

Molecules

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In the present work, the formation of the four-membered cyclic nitronates and the retro (3 + 2) cycloaddition (retro-32CA) reaction of the 4H-[1,2]oxazete 2-oxide were studied using the density functional theory method at the MPWB1K/6-311G(d,p) theoretical level. The electronic structure of 3-tert-butyl-4,4-dimethyl-1,2-dinitro-pent-2-ene was known through electron localization function analysis, natural population analysis, and molecular electrostatic potential analysis. The formation of 4,4-di-tert-butyl-3-nitromethyl-4H-[1,2]oxazete 2-oxide proceeds through a one-step mechanism. The mechanism of the retro-32CA leading to di-tert-butyl ketone and nitrile oxide derivative should be described as an asynchronous two-stage one-step process. The bonding evolution theory study was carried out to clarify the mechanisms of the formation of 4H-[1,2]oxazete 2-oxide and their retro-32CA.

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Section: Computational Detailssupporting

confidence: 73%

The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

Kącka‐Zych

2021

Molecules

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“…The most universal methodology for preparing nitrofunctionalized cyclic compounds is cycloaddition reactions involving respective conjugated nitroalkenes (CNA) [4,11]. In this way, several four- [12,13], five - [14][15][16][17], and six-membered [18][19][20][21] nitro-cycles have been prepared. This is possible via [2 + 2], [3 + 2], and [4 + 2] cycloadditions, respectively.…”

Section: Introductionmentioning

confidence: 99%

Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

Alnajjar

Jasiński

2019

J Mol Model

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The competition between [2 + 1] and [4 + 1] channels regarding reactions of conjugated nitroalkenes with dichlorocarbene was explored based on B3LYP/6-31G(d) calculations. It was found that, in the case of cycloadditions involving parent nitroethene and its 1-substituted analogs, the [2 + 1] scheme should be treated as possible only from the kinetic process point of view. On the other hand, in similar reactions involving 2-substituted nitroethenes, both channels considered may compete. Additionally, mechanistic aspects of all cycloadditions were analyzed. It was found that the considered [2 + 1]-cycloadditions proceed via a non-polar mechanism with a biradicaloidal transition state (TS), whereas [4 + 1]-cycloadditions proceed via a polar mechanism with a zwitterionic TS.

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“…The quantum chemical calculation performed at the M062x/LANL2DZ theoretical level [27,28], which is specially dedicated to precise energetic considerations and has recently been applied in the simulation of energetic and structural analyses of molecules with similar structural moieties [29,30,31,32,33], allows us to compare the geometry of the molecules of phosphines 6 , their dioxides and complexes that were not crystallised in crystals, well-measurable by a single crystal X-ray diffraction. The geometry optimisation for the structure [Pd( 6q )Cl 2 ] was therefore performed and the obtained geometry parameters of [Pd( 6q )Cl 2 ] calc were compared with those received from the X-ray diffraction experiments for [Pd( 6q )Cl 2 ] xray .…”

Section: Resultsmentioning

confidence: 99%

New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

et al. 2019

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A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the starting material. The palladium complexes of new ligands were obtained and characterised on the example of a crystalline dichloropalladium complex of [(1R,2R,9S,10S,11R,12R)-4-phenyltetracyclo[8.2.1.02,9.03,8]trideca-3,5,7-triene-11,12-diyl]bis(diphenylphosphane). A notably high activity and stereoselectivity of the palladium catalysts based on the new ligands were confirmed in a model asymmetric allylic substitution reaction. Herein, we discuss the geometry of the palladium complexes formed and its impact on the efficiency of the catalysts. A comparison of their geometric features with other bis(phosphane) ligand complexes found in the Cambridge Structural Database and built density functional theory (DFT) commutated models is also presented and rationalised.

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Regiospecific formation of the nitromethyl-substituted 3-phenyl-4,5-dihydroisoxazole via [3 + 2] cycloaddition

Cited by 19 publications

References 43 publications

The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

Competition between [2 + 1]- and [4 + 1]-cycloaddition mechanisms in reactions of conjugated nitroalkenes with dichlorocarbene in the light of a DFT computational study

New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

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