The 1,3-Dipolar Cycloaddition of 3-Methyl-5-phenylisoxazoline N-Oxides

Chow, Yuan L.; Shu, Yu; Bakker, Bert H.; Pillay, K. S.

doi:10.3987/com-88-s17-1

Cited by 11 publications

(4 citation statements)

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“…Several methods have been used for the synthesis of these heterocycles, such as asymmetric synthesis [ 6–8 ] (path a‐c), condensation of α‐nitroesters with aldehydes [ 9 ] (path d), o‐alkylation of nitroante anions with (α‐tosylvinyl)phosphonates [ 10 ] (path e), or stepwise condensation of a β‐bromo‐sulfonium salt and nitroethane [ 11 ] (path f) (Scheme 1). Although many synthetic methods have been developed, [ 12–15 ] practical protocols for the enantioselective construction of isoxazoline N‐oxides are very limited.…”

Section: Introductionmentioning

confidence: 99%

“…One of the fundamental goals for understanding a given chemical rearrangement is to analyze the changes of quantum mechanical observables such as the electron density along the reaction pathway. This approach enables a comprehensive picture of the chemical reactivity in terms of how and S C H E M E 1 Synthesis methods of isoxazoline N-oxide derivatives [6][7][8][9][10][11] S C H E M E 2 Reaction of nitroalkenes (1a, 1b) with dimethyl bromomalonate (2) S C H E M E 3 Two competitive pathways for reactions of nitroalkenes (1a, 1b) with carbene (2) when chemical events, for example, bond rupture and formation processes, will take place. To this end, the bonding evolution theory (BET) is used, [17] which combines the topological analysis of the electron localization function (ELF).…”

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confidence: 99%

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Understanding the uniqueness of the stepwise [4 + 1] cycloaddition reaction between conjugated nitroalkenes and electrophilic carbene systems with a molecular electron density theory perspective

Kącka‐Zych

2020

Int J of Quantum Chemistry

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The [4 + 1] cycloaddition (41CA) and [2 + 1] cycloaddition (21CA) reactions of the α-halogeno-nitroalkenes with carbene have been studied using the molecular electron density theory through density functional theory calculations at the MPWB1K(PCM)/ 6-311G(d,p) computational level. The 41CA reaction take place through a polar twostep mechanism involving the formation of a zwitterionic intermediate. The competitive 21CA reaction path proceeds according to nonconcerted two-stage one-step. Bonding evolution theory analysis of 41CA reaction allows the distinguishing of four groups along the reaction path. The reaction begins with rupture of the C C double bond of the alkene moiety and formation of the pseudoradical center. Formation of the O C and C C new single bonds begins in subsequent phases. In the last stage of the 41CA reaction path, we observed the formation of an N C new double bond. In the case of 21CA reaction path, we observed the successive rupture of the C C double bond of the alkene moiety, formation of C C new single bond and pseudoradical center, and creation of a second C C single bond.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Understanding the uniqueness of the stepwise [4 + 1] cycloaddition reaction between conjugated nitroalkenes and electrophilic carbene systems with a molecular electron density theory perspective

Kącka‐Zych

2020

Int J of Quantum Chemistry

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“…On the other hand, 1,1-bisnucleophiles C such as 1,3-dicarbonyl compounds, cyanoacetates or nitroacetates lead to polysubstituted cyclopropanes E. 4 However, application of substrates bearing one EWG-group such as aliphatic nitro compounds in such transformations is scarcely documented. 5 We envisioned such bis-nucleophilic synthons as primary nitro compounds as viable reaction partners for vinyl sulfonium salts. Nitronate anions are well-known ambident nucleophiles.…”

Section: Introductionmentioning

confidence: 99%

“…4 However, application of substrates bearing one EWG-group such as aliphatic nitro compounds in such transformations is scarcely documented. 5…”

Section: Introductionmentioning

confidence: 99%