Progress in 1,3-dipolar cycloadditions in the recent decade: an update to strategic development towards the arsenal of organic synthesis

Singh, Maya Shankar; Chowdhury, Sushobhan; Koley, Suvajit

doi:10.1016/j.tet.2016.02.031

Cited by 167 publications

(54 citation statements)

References 280 publications

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“…[1] Since the seminali nvestigations of Huisgen,[2] ag reat deal of research has been performed not only to extend the scope of these useful annulation processes but also to ascertain whether the exact mechanism of action is based on concerted or nonconcerted events. [1] Since the seminali nvestigations of Huisgen,[2] ag reat deal of research has been performed not only to extend the scope of these useful annulation processes but also to ascertain whether the exact mechanism of action is based on concerted or nonconcerted events.…”

Section: Introductionmentioning

confidence: 99%

A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI‐IMS‐MS and DFT Studies

Lespes

Pair

Maganga

et al. 2018

Chemistry A European J

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The fragile intermediates of the domino process leading to an isoxazolidin-5-one, triggered by unique reactivity between Meldrum's acid and an N-benzyl nitrone in the presence of a Brønsted base, were determined thanks to the softness and accuracy of electrospray ionization mass spectrometry coupled to ion mobility spectrometry (ESI-IMS-MS). The combined DFT study shed light on the overall organocatalytic sequence that starts with a stepwise (3+2) annulation reaction that is followed by a decarboxylative protonation sequence encompassing a stereoselective pathway issue.

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Section: Introductionmentioning

confidence: 99%

A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI‐IMS‐MS and DFT Studies

Lespes

Pair

Maganga

et al. 2018

Chemistry A European J

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“…Structural diversification can be achieved in such processes by simple and systematic variations in each starting material (Dö mling & Ugi, 2000;Dö mling, 2006). Cycloaddition reactions are of key importance in organic synthesis for building molecular frameworks, and for the construction of nitrogen heterocycles, such as chiral pyrrolidines, the preferred method is 1,3-dipolar cycloaddition of azomethine ylide to electron-deficient alkenes (Falorni et al, 1998;Pandey et al, 2006;Boruah et al, 2007;Singh et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of spiro[indoline-3,3′-pyrrolizines] by 1,3-dipolar reactions between isatins, L-proline and electron-deficient alkenes

et al. 2017

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Two spiro[indoline-3,3'-pyrrolizine] derivatives have been synthesized in good yield with high regio- and stereospecificity using one-pot reactions between readily available starting materials, namely L-proline, substituted 1H-indole-2,3-diones and electron-deficient alkenes. The products have been fully characterized by elemental analysis, IR and NMR spectroscopy, mass spectrometry and crystal structure analysis. In (1'RS,2'RS,3SR,7a'SR)-2'-benzoyl-1-hexyl-2-oxo-1',2',5',6',7',7a'-hexahydrospiro[indoline-3,3'-pyrrolizine]-1'-carboxylic acid, CHNO, (I), the unsubstituted pyrrole ring and the reduced spiro-fused pyrrole ring adopt half-chair and envelope conformations, respectively, while in (1'RS,2'RS,3SR,7a'SR)-1',2'-bis(4-chlorobenzoyl)-5,7-dichloro-2-oxo-1',2',5',6',7',7a'-hexahydrospiro[indoline-3,3'-pyrrolizine], which crystallizes as a partial dichloromethane solvate, CHClNO·0.981CHCl, (II), where the solvent component is disordered over three sets of atomic sites, these two rings adopt envelope and half-chair conformations, respectively. Molecules of (I) are linked by an O-H...·O hydrogen bond to form cyclic R(48) hexamers of \overline{3} (S) symmetry, which are further linked by two C-H...O hydrogen bonds to form a three-dimensional framework structure. In compound (II), inversion-related pairs of N-H...O hydrogen bonds link the spiro[indoline-3,3'-pyrrolizine] molecules into simple R(8) dimers.

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“…The 1,3-DC reactions between 1,3-dipoles and dipolarophiles are among the most important and extensively studied reactions in organic chemistry [40][41][42][43][44][45] recognized for their generality, scope, and mechanism, the judgment must be different" 47 .…”

Section: On the Reaction Mechanism Of 13-dipolar Cycloadditionsmentioning

confidence: 99%

On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate

Adjieufack

Ndassa

Patouossa

et al. 2017

Phys. Chem. Chem. Phys.

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In this work we report on the progress that has been made towards gaining an understanding of the molecular mechanism of 1,3-dipolar cycloadditions using the bonding evolution theory (BET). A detailed analysis of the flow of electron density along the reaction pathway of the formal 1,3-dipolar cycloaddition reaction between cyclic nitrones (pyrroline-1-oxide and 2,3,4,5 tetrahydropyridine-1-oxide) and ethyl acrylate, as a case study, allowed the nature of the molecular mechanisms to be characterized.The present study provides a deep insight into the reaction mechanism, based on the electron density rearrangements given by the structural stability domains, and their connection with the bond breaking/forming processes along the reaction pathway.Electron pushing formalism is a powerful tool to describe chemical reactivity. Here, we show how the Lewis structures can be recovered and how curly arrows describe electron density transfers in chemical reaction mechanisms based on the BET results. The reaction mechanism is described by four consecutive events taking place as the reaction progresses: 1) the population of the initial N−C double bond is transferred to the N and C atoms; 2) the population of the initial double C-C bond is transferred to the C atoms.Along the ortho pathway the next steps are: 3) the C−C bond-forming, and 4) the O-C 2 bond-forming process. The order of 3) and 4) is inverted in the meta channel. Based on the sequence of the structural stability domains along the intrinsic reaction coordinate, a new synchronicity index is proposed, allowing us to classify and quantify the (a)synchronicity of the 1,3-DC reactions and, therefore, the nature of the reaction mechanism.3

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Progress in 1,3-dipolar cycloadditions in the recent decade: an update to strategic development towards the arsenal of organic synthesis

Cited by 167 publications

References 280 publications

A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI‐IMS‐MS and DFT Studies

A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI‐IMS‐MS and DFT Studies

Synthesis of spiro[indoline-3,3′-pyrrolizines] by 1,3-dipolar reactions between isatins, L-proline and electron-deficient alkenes

On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate

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