Non-classical CH⋯O hydrogen-bond determining the regio- and stereoselectivity in the [3 + 2] cycloaddition reaction of (Z)-C-phenyl-N-methylnitrone with dimethyl 2-benzylidenecyclopropane-1,1-dicarboxylate. A topological electron-density study

Nacereddine, Abdelmalek Khorief; Sobhi, Chafia; Djerourou, Abdelhafid; Ríos‐Gutiérrez, Mar; Domingo, Luís R.

doi:10.1039/c5ra20268j

Cited by 40 publications

(20 citation statements)

References 57 publications

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“…[37] NCI analysis is used to predict the attractive and repulsive interactions between the reactant molecules. [31,44,45] These interactions are based on the electron density and the second eigenvalue (λ2) of the Hessian of the electron density. This method provides 2D and 3D NCI plots, which are indicative of the types of interactions for a reaction.…”

Section: Resultsmentioning

confidence: 99%

Revealing the Origin of Π‐facial and Regioselectivity in the Diels‐Alder Reaction of Unsymmetrical, Cage‐annulated 1,3‐Cyclohexadiene with Ethyl Propiolate Dienophile: a DFT Study

Patel

Ganguly

2020

ChemistrySelect

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DFT [M06-2X/6-31 + G(d,p) and MPWB1 K/6-311G(d)] calculations have elucidated the origins of π-facial and regioselectivity in the Diels-Alder reactions of hexacyclo [7.5.1.0 1,6 .0 6,13 .0 8,12 .0 10,14 ] pentadeca-2,4-diene-7,15-dione (HPDD) and hexacyclo [7.5.2.0 1,6 .0 6,13 .0 8,12 .0 10,14 ] hexadeca-2,4-diene-7,16-dione (HHDD) dienes with ethyl propiolate (EP) as the dienophile. The origin of π-facial stereoselectivity of these Diels-Alder reactions has been rationalized with molecular electrostatic potential (MESP), potential energy surface (PES), and Non-Covalent Interaction (NCI). The role of the steric effect on the π-facial stereoselectivity of these Diels-Alder reactions has also been observed. The origin of distal/proximal regioselectivity of HHDD with EP was explained by attractive Non-Covalent Interaction (NCI) and electrostatic repulsion. This is one of the rare examples in Diels-Alder reaction with both the π-facial stereoselectivity and the regioselectivity with single diene and dienophile.

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Section: Resultsmentioning

confidence: 99%

Revealing the Origin of Π‐facial and Regioselectivity in the Diels‐Alder Reaction of Unsymmetrical, Cage‐annulated 1,3‐Cyclohexadiene with Ethyl Propiolate Dienophile: a DFT Study

Patel

Ganguly

2020

ChemistrySelect

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“…Very recently, we have shown that the nonclassical CH–O HB formation between a carboxylate oxygen atom of the ethylene derivative and the nitrone C–H hydrogen atom determines the regioselectivity and stereoselectivity in the 32CA reaction of (Z)‐ C ‐phenyl‐ N ‐methylnitrone with dimethyl 2‐benzylidenecyclopropane‐1,1‐dicarboxylate. NCI analysis of the most favorable ortho / endo TS revealed the formation of this nonclassical CH–O HB . Consequently, to be able to prove the stabilization of the endo TSs by the formation of the HB and to explain the preference of the meta/endo reactive pathway over the ortho/endo one, an NCI analysis of the mentioned TSs was performed.…”

Section: Resultsmentioning

confidence: 99%

A DFT study of the mechanism and selectivities of the [3 + 2] cycloaddition reaction between 3‐(benzylideneamino)oxindole and trans‐β‐nitrostyrene

Sobhi

Nacereddine

Djerourou

et al. 2016

J of Physical Organic Chem

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The mechanism and regioselectivities and stereoselectivities of the [3 + 2] cycloaddition (32CA) reaction of 3-(benzylideneamino) oxindole (AY) and trans-βnitrostyrene have been studied using both B3LYP and ωB97XD density functional theory methods together with the standard 6-31G(d) basis set. Four reactive pathways associated with the ortho and meta regioselective channels and endo and exo stereoselective approaches modes have been explored and characterized. While the B3LYP functional fails to predict the experimental regioselectivity, the ωB97XD one succeeds to predict the experimentally observed meta regioselectivity favoring the formation of meta/endo cycloadduct as the major isomer. Inclusion of solvent effects increases the regioselectivity and decreases the experimentally observed stereoselectivity. Analysis of the density functional theory global reactivity indices and the Parr functions of the reagents in its ground state allows explaining the reactivity and the meta regioselectivity of this zwitterionic-type 32CA reaction, which account for the high polar character of this reaction. Non-covalent interaction analysis of the most favorable meta/endo transition state structure reveals that the formation of a hydrogen-bond between 1 nitro oxygen and the AY N-H hydrogen is responsible for the selectivity experimentally found in this polar zwitterionic-type 32CA reaction.

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“…BET is the joint use of ELF and Thom's CT to demonstrate the molecular mechanism of a reaction in terms of creation or annihilation of electronic domains. The molecular mechanism of chemical reactions including Diels−Alder cycloaddition reaction [14][15][16][17][18][19][20][21][22][23][24][25][26] , cyclization reaction 27,28 , Nazarov reaction 29 , SN2 reaction 3 , Cope and Claisen rearrangements [30][31][32] , Friedel−Crafts reaction 33 , Staudinger reaction 34,35 , ene reaction 36,37 , ring cleavage reaction 38,39 , trimerization reaction 40 , [3 + 2] cycloaddition reaction 10,24,[41][42][43][44][45][46][47][48] , and [2 + 2] cycloaddition reaction 49,50 have been studied in the BET framework. BET analysis has revealed that in some reactions the electron density does not flow in a cyclic, one−way curve meaning that evolution of chemical bonds are out a pericyclic mechanism 15,16,31 .…”

Section: Introductionmentioning

confidence: 99%

Following the Molecular Mechanism of Decarbonylation of Unsaturated Cyclic Ketones Using Bonding Evolution Theory Coupled with NCI Analysis

2017

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The synergetic use of bonding evolution theory (BET) and noncovalent interaction (NCI) analysis allows to obtain new insight into the bond breaking/forming processes and electron redistribution along the reaction path to understand the molecular mechanism of a reaction and recognize regions of strong and weak electron pairing. This viewpoint has been considered for cheletropic extrusion of CO from unsaturated cyclic ketones cyclohepta-3,5-dien-1-one CHD, cyclopent-3-en-1-one CPE, and bicyclo[2.2.1]hept-2-en-7-one BCH by using hybrid functional MPWB1K in conjugation with aug-cc-pVTZ basis set. Decarbonylation of CHD, CPE, and BCH are nonpolar cyclo-elimination reactions that are characterized by the sequence of turning points (TPs) as CHD, 1-11-C[CC]CCFFFCCC-0:HT + CO; CPE, 1-8-CC[CCF][FF][FF]F[CC]-0:BD + CO; and BCH, 1-8-CC[CC]F[FF]F[CC]-0:CD + CO. Breaking of C-C bond between the terminal carbon atoms of diene/triene framework and carbon atom of CO fragment starts at a distance of ca. 1.9-2.0 Å in the vicinity of the transition structure where the transition states are not reached yet. NCI analysis explains that the noncovalent interactions between two fragments appeared after the breaking of C-C bonds.

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Non-classical CH⋯O hydrogen-bond determining the regio- and stereoselectivity in the [3 + 2] cycloaddition reaction of (Z)-C-phenyl-N-methylnitrone with dimethyl 2-benzylidenecyclopropane-1,1-dicarboxylate. A topological electron-density study

Abstract: Formation of a non-classical CH⋯O hydrogen-bond involving the nitrone C–H hydrogen is responsible for the selectivity experimentally found in this non-polar zw-type 32CA reaction.

Cited by 40 publications

References 57 publications

Revealing the Origin of Π‐facial and Regioselectivity in the Diels‐Alder Reaction of Unsymmetrical, Cage‐annulated 1,3‐Cyclohexadiene with Ethyl Propiolate Dienophile: a DFT Study

Revealing the Origin of Π‐facial and Regioselectivity in the Diels‐Alder Reaction of Unsymmetrical, Cage‐annulated 1,3‐Cyclohexadiene with Ethyl Propiolate Dienophile: a DFT Study

A DFT study of the mechanism and selectivities of the [3 + 2] cycloaddition reaction between 3‐(benzylideneamino)oxindole and trans‐β‐nitrostyrene

Following the Molecular Mechanism of Decarbonylation of Unsaturated Cyclic Ketones Using Bonding Evolution Theory Coupled with NCI Analysis

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