1, 3-Dipolar cycloaddition reactions of selected 1,3-dipoles with 7-isopropylidenenorbornadiene and follow-up thermolytic cleavage: A computational study

Arhin, Grace; Adams, Anita Houston; Opoku, Ernest; Tia, Richard; Adei, Evans

doi:10.1016/j.jmgm.2019.08.004

Cited by 26 publications

(13 citation statements)

References 30 publications

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“…The default self-consistency field (SCF) convergence criteria (SCF=Tight) within the Gaussian 16 quantum chemistry program was used [24,25]. Intrinsic reaction coordinate calculations [25][26][27] were then performed to ensure that each TS smoothly connects the reactants and products along the reaction coordinate [28][29][30]. We used the CYLview for visualization and illustration of all the optimized structures [31].…”

Section: A Dft Calculations and Geometry Optimizationsmentioning

confidence: 99%

“…(3 + 2) and Diels-Alder cycloaddition reactions are common cycloaddition reactions that provide efficient methods for constructing vital heterocyclic and carbocyclic compounds [1][2][3][4]. The synthetic applicability of (3 + 2) cycloaddition (32CA) reactions in modern-day chemistry is overwhelming [5,6]. The exact mechanistic peculiarity of a particular 32CA reaction depends critically on a delicate interplay of several factors, primarily the electronic and steric nature of the substituents on the reacting species [7,8].…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Studies on the Reactions of Aryl and Hetaryl Thioketones with Nitrilimines

Gb¹,

Opoku

2021

Preprint

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Many synthetic routes to constructing biologically-active heterocyclic compounds are made feasible through the (3 + 2) cycloaddition 32CA reactions. Due to a large number of possible combinations of several heteroatoms from either the three-atom components (TACs) or the ethylene derivatives, the potential of the 32CA reactions in heterocyclic syntheses is versatile. Herein, the 32CA of thiophene-2-carbothialdehyde derivatives and C,N-disubstituted nitrilimines have been studied through density functional theory (DFT) calculations at the B3LYP/6-311G(d,p) level of theory. In the present study, one-step (3 + 2) and two-step (4 + 3) mechanisms of the addition of the TAC and ethylene derivative have been investigated. In all reactions considered, the one-step (3 + 2) cycloaddition is preferred over the two-step (4 + 3) cycloaddition. The TAC chemoselectively adds across the thiocarbonyl group present in the ethylene derivative in a (3 + 2) fashion to form the corresponding cycloadduct. Analysis of the electrophilic ( and nucleophilic ( Parr functions at the various reaction centers in the ethylene derivative show that the TAC adds across the atomic centers with the largest Mulliken atomic spin densities, which is in total agreement with the experimental observation. The selectivities observed in the title reaction are kinetically controlled.

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Section: A Dft Calculations and Geometry Optimizationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Studies on the Reactions of Aryl and Hetaryl Thioketones with Nitrilimines

Gb¹,

Opoku

2021

Preprint

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“…Very recently, two different studies [20,21] have addressed the regio-, stereo-, and enantioselectivities of the 32CA reactions of 7-isopropylidenenorbornadiene and oxonorbornadiene with nitrones, azides, and nitrileimines.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

2021

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The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD), with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity, have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G (d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol−1 in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study establishes the depopulation of the N–N–C core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration.

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“…Particularly when an acyclic nitrone (N-methyl-C-phenylnitrone) was employed, the reaction was 100% regioselective with respect to attack on the highly hindered side of the dipolarophile. Also, Arhin et al [13] reported a theoretical study on the reactivity and selectivities in the reaction of 7-isopropylidenenorbornadiene with N-methyl-Cphenylnitrone and phenyl azide by examining the energetics of the various elementary steps involved in the productive reaction channels as well as various routes leading to minor adducts. Their study provided rationalization of the general reactivity and selectivities in the reaction of 7-isopropylidenenorbornadiene with N-methyl-C-phenylnitrone and phenyl azide.…”

Section: Introductionmentioning

confidence: 99%

Regio‐, stereo‐, and site‐selectivities of 1,3‐dipolar Cycloaddition reaction of benzonitrile oxide with unsymmetrically substituted norbornenes and norbornadienes: A computational study

Abdullah

Tia

Adei

2021

J of Physical Organic Chem

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In this computational study, density functional theory (DFT) calculations at the M06/6-311G(d,p) level of theory were employed to study the regio-, stereo-, and site-selectivities of 1,3-dipolar cycloadditions of benzonitrile oxide (BNO) with unsymmetrically substituted norbornenes and norbornadienes. The reactions between BNO and unsymmetrically-substituted 2-norbornes and unsymmetrically-substituted 2-norbornadienes proceed with the oxygen of the BNO attacking the more hindered side of the double bond in all cases except when strong EWGs are introduced. For the reaction between BNO and unsymmetrically-substituted 2-norbornadienes, varying degrees of selectivities are observed depending on the substituent, indicating that site-selectivity is largely influenced by nature of substituents. Generally, the regio-isomers in

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1, 3-Dipolar cycloaddition reactions of selected 1,3-dipoles with 7-isopropylidenenorbornadiene and follow-up thermolytic cleavage: A computational study

Cited by 26 publications

References 30 publications

Theoretical Studies on the Reactions of Aryl and Hetaryl Thioketones with Nitrilimines

Theoretical Studies on the Reactions of Aryl and Hetaryl Thioketones with Nitrilimines

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

Regio‐, stereo‐, and site‐selectivities of 1,3‐dipolar Cycloaddition reaction of benzonitrile oxide with unsymmetrically substituted norbornenes and norbornadienes: A computational study

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