Nucleophilic addition to nitrile oxides: concerted or stepwise?

Nguyen, Minh Tho; Malone, Seamus; Hegarty, A. F.; Williams, Ian H.

doi:10.1021/jo00011a044

Cited by 24 publications

(1 citation statement)

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“…[37,42] The multiconfiguration selfconsistent field calculations performed by McDouall et al [43] were more precise and firmly supported this transformation's concerted nature. [37,43] According to Nguyen et al, [44,45] Huisgen reactions are normally considered to proceed as concerted reactions. In summary, the quantummechanical analysis come to the conclusion that Huisgen reactions in general proceed as concerted processes in accordance with experimental results.…”

Section: The Mechanistic Aspects and Regioselectivitymentioning

confidence: 99%

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Almutaleb

Al‐abbasi

2022

J of Physical Organic Chem

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In this article, we present advances related to 1,3‐dipolar cycloadditions of generated pyridinium ylides and apply these results to specific 1,3‐dipolar cycloaddition reactions with oxindole dipolarophiles. The ylide discussed in this article is generated from alkylation reactions between substituted pyridines and a primary electrophile. Cycloaddition reactions proceeding from pyridinium ylides and various oxindoles are reported with good stereo‐ and regioselectivity. Cycloaddition reactions take place by the overlap of the HOMO of the dipole and the LUMO of the dipolarophile when the two orbitals have similar energies, resulting in the formation of two new bonds. To get more insight into the reaction nature, a quantum chemical simulation was performed. A computational study is performed on the reactants (pyridinium ylides and oxindoles) and resulting cycloadducts. The present analysis reveals that the cycloaddition reactions under study can be classified in the normal electron demand category. Regioselectivity and mechanism of 1,3‐cycloaddition reactions are studied in the light of several theoretical approaches such as activation energy, Houk's rule based on the FMO theory, and the DFT reactivity indices.

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Section: The Mechanistic Aspects and Regioselectivitymentioning

confidence: 99%

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Almutaleb

Al‐abbasi

2022

J of Physical Organic Chem

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Synthesis of Six- to Nine-Membered Ring Oximinoorthodithiolactones by Cyclization of NitroketeneS,S-Acetals in Trifluoromethanesulfonic Acid

Coustard

2001

Eur. J. Org. Chem.

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Synthesis of 3‐Methoxy‐16α‐nitro‐14,17‐ethenoestra‐1,3,5(10)‐trien‐17β‐yl Acetate and Fragmentation‐Mediated Pathways to 14β,15β‐Fused N‐Heterocycles and 14β‐Functionalised Alkyl Derivatives

2007

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The Diels–Alder reaction of 3‐methoxyestra‐1,3,5(10),14,16‐pentaen‐17‐yl acetate (1) with nitroethylene gives 3‐methoxy‐16‐nitro‐14,17‐ethenoestra‐1,3,5(10)‐trien‐17β‐yl acetate (2). Cycloadduct 2 can be reduced with TiCl3, giving oxazine 3 as a result of sigmatropic rearrangement, whereas the treatment of 2 with Lewis acids (TiCl4, SnCl4) leads to a derivative of the cyclic hydroximic acid 10; the latter is viewed as a product of intramolecular rearrangement. Cycloadduct 2 suffers a weak base‐induced cleavage of the C(16)–C(17) bond, releasing the nitrile oxide intermediate, which can be trapped by a dipolarophile or reduced with triphenylphosphane. Thus, the trapping of the nitrile oxide with propargyl alcohol gives the isoxazole 12 in 50 % yield, and the reduction of the nitrile oxide with triphenylphosphane gives nitrile 9 in 94 % yield. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Nucleophilic addition to nitrile oxides: concerted or stepwise?

Cited by 24 publications

References 2 publications

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Synthesis of Six- to Nine-Membered Ring Oximinoorthodithiolactones by Cyclization of NitroketeneS,S-Acetals in Trifluoromethanesulfonic Acid

Synthesis of 3‐Methoxy‐16α‐nitro‐14,17‐ethenoestra‐1,3,5(10)‐trien‐17β‐yl Acetate and Fragmentation‐Mediated Pathways to 14β,15β‐Fused N‐Heterocycles and 14β‐Functionalised Alkyl Derivatives

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Nucleophilic addition to nitrile oxides: concerted or stepwise?

Cited by 24 publications

References 2 publications

Synthesis, characterization and computational studies for (2′S*,3R*,3′S*,8a′R*)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Synthesis, characterization and computational studies for (2′S*,3R*,3′S*,8a′R*)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Synthesis of Six- to Nine-Membered Ring Oximinoorthodithiolactones by Cyclization of NitroketeneS,S-Acetals in Trifluoromethanesulfonic Acid

Synthesis of 3‐Methoxy‐16α‐nitro‐14,17‐ethenoestra‐1,3,5(10)‐trien‐17β‐yl Acetate and Fragmentation‐Mediated Pathways to 14β,15β‐Fused N‐Heterocycles and 14β‐Functionalised Alkyl Derivatives

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Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives