Aziridination of Aromatic Aldimines Through Stabilized Ammonium Ylides: A Molecular Electron Density Theory Study

Emamian, Saeedreza; Domingo, Luís R.; Ríos‐Gutiérrez, Mar; Zahedi, Ehsan; Hosseini, S. J. F.

doi:10.1002/ejoc.201801763

Cited by 4 publications

(3 citation statements)

References 54 publications

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“…It should also be pointed out that, similar to the trans pathway, the ring closure step is the RDS within the cis pathway. Note, however, that in the aziridination reaction recently studied by Emamian and coworkers , the RDS is the ring closure step.…”

Section: Resultsmentioning

confidence: 99%

“…There are few theoretical studies on aziridination reaction that have fully studied energy transformation, selectivities, and mechanistic aspects. Very recently, Emamian and coworkers reported a molecular electron density theory (MEDT) study on the stereoselective aziridination of aromatic aldimines through stabilized ammonium ylides. This investigation demonstrated that the reaction under study takes place at highly trans ‐stereoselectivity, in excellent agreement with experimentally findings , and the ring closer step is the rate‐determining step (RDS).…”

Section: Introductionmentioning

confidence: 99%

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Hexamethylphosphanetriamine‐mediated aziridination of imines with alpha‐ketoesters: A molecular electron density theory study

Amiri

Emamian

Hosseini

et al. 2020

J of Physical Organic Chem

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The highly trans‐stereoselective reaction of oxyphosphonium enolate (OPE) with N‐benzylidene‐4‐methoxybenzenesulfonamide (N‐BMS) in toluene, at room temperature leading to trans‐aziridine‐2‐carboxylate (trans‐Az 3), was theoretically studied using molecular electron density theory (MEDT) at the B3LYP/6‐31G(d) computational level to shed light on the energy transformation, selectivities, and mechanistic aspects. This domino process is initialized by adding of N,N,N′,N′,N″,N″‐hexamethylphosphanetriamine (HMPT) to methyl benzoylformate to generate OPE. Subsequently, nucleophilic addition of OPE to the C–N double bond in N‐BMS leads to the intermediate IN‐Ta. Finally, trans‐Az 3 is formed through a 3‐exo‐tet ring closure step as a result of the nucleophilic attack of the negatively charged nitrogen atom on the carbon atom bearing –OP (NMe2)3 in IN‐Ta. Analysis of the relative Gibbs free energies shows that the ring closure step is the rate‐determining step. By an investigation of the conceptual density functional theory reactivity indices, OPE and N‐BMS are classified as a strong nucleophilic and as a strong electrophilic species, respectively, which indicates that the additional step of OPE to N‐BMS should display a high‐polar character. An analysis of the calculated electrophilic and nucleophilic Parr functions at the reactive sites of reagents clarifies the regioselectivity observed experimentally along the C1–C2 bond formation process.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hexamethylphosphanetriamine‐mediated aziridination of imines with alpha‐ketoesters: A molecular electron density theory study

Amiri

Emamian

Hosseini

et al. 2020

J of Physical Organic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…Very recently, Emamian et al reported a molecular electron density theory (MEDT) study to analyze stereoselective aziridination of aromatic aldimines through stabilized ammonium ylides. Their investigation showed that the reaction under study progress at highly trans ‐stereoselectivity, in excellent agreement with experimentally findings, and its ring closer step is the rate‐determining step (RDS).…”

Section: Introductionmentioning

confidence: 99%

Stereoselective aziridination of imines via ammonium ylides: A molecular electron density theory study

Jalali

Hosseini

Ali‐Asgari

et al. 2019

Journal of Heterocyclic Chem

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The highly trans-stereoselective reaction of ammonium salt (AS 2) toward (E)-Nbenzylidene-4-methylbenzenesulfonamide (IM 4) in the presence of Na 2 CO 3 leading to an aziridine derivative, trans-Az 6, was theoretically studied using Molecular Electron Density Theory (MEDT) at the B3LYP/6-31G(d) computational level to probe energy transformation, selectivities, and molecular mechanism. The reaction starts by a nucleophilic substitution reaction between 1,4diazabicyclo [2.2.2]octane (DABCO) and phenacyl bromide (PB) to form AS 2 which undergoes a proton abstraction by Na 2 CO 3 to produce Ammonium Ylide (AY 3). Subsequently, nucleophilic addition of AY 3 to the double bond in IM 4 leads to form a betaine-like intermediate, namely, IN-Ta which named IN-Ta. Finally, trans-Az 6 is produced as a result of the nucleophilic attack of the negatively charged nitrogen atom on the carbon atom bearing DABCO in IN-Ta.Analysis of the relative Gibbs free energies shows that the ring closure step is the rate-determining step (RDS). By an investigation of the conceptual density functional theory, CDFT reactivity indices AY 3 and IM 4 are classified as a strong nucleophilic molecular system and as a strong electrophilic molecular system, respectively, which implies that the addition step of AY 3 to IM 4 has a high polar character. An analysis of the calculated electrophilic and nucleophilic Parr functions at the reactive sites of reagents clarifies the regioselectivity observed experimentally within the C 1 -C 2 bond creation process.

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Cascade synthetic strategies opening access to medicinal-relevant aliphatic 3- and 4-membered N-heterocyclic scaffolds

Łowicki

Przybylski

2022

European Journal of Medicinal Chemistry

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Aziridination of Aromatic Aldimines Through Stabilized Ammonium Ylides: A Molecular Electron Density Theory Study

Cited by 4 publications

References 54 publications

Hexamethylphosphanetriamine‐mediated aziridination of imines with alpha‐ketoesters: A molecular electron density theory study

Hexamethylphosphanetriamine‐mediated aziridination of imines with alpha‐ketoesters: A molecular electron density theory study

Stereoselective aziridination of imines via ammonium ylides: A molecular electron density theory study

Cascade synthetic strategies opening access to medicinal-relevant aliphatic 3- and 4-membered N-heterocyclic scaffolds

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