Arylazide Cycloaddition to Methyl Propiolate: DFT‐Based Quantitative Prediction of Regioselectivity

Molteni, Giorgio; Ponti, Alessandro

doi:10.1002/chem.200204681

Cited by 64 publications

(38 citation statements)

References 47 publications

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“…They used this approach to investigate cycloadditions of C-carbomethoxy-N-(4-substituted)phenylnitrilimines 2.10, aryl azides 2.11, and (4-substituted)benzonitrile oxides 2.12 with methyl propiolate 2.13 shown in Scheme 6. [32][33][34][35] The DW values correctly predict the preferred regiochemistry preference for all reactions considered. The authors also showed that DDW is proportional to the barrier heights and this correlation can be used to estimate product ratios between the regioisomers.…”

Section: Conceptual Density Functional Theory (Dft) and Hard And Softmentioning

confidence: 95%

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

2006

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Abstract:The application and performance of conceptual and qualitative theories and quantitative quantum mechanical methods to the study of mechanism, reactivity, and selectivity of 1,3-dipolar and Diels-Alder cycloadditions are reviewed. This review emphasizes the application of conceptual density functional theory (DFT) for predicting reactivity and regioselectivity, and highly accurate quantum mechanical methods for predicting barrier heights and reaction energetics. Applications of computations to solvation effects, metal and organocatalysis, are also described.

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Section: Conceptual Density Functional Theory (Dft) and Hard And Softmentioning

confidence: 95%

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

2006

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“…Overall, this results in a rate acceleration of 10 5 and an absolute regioselectivity of the Cu I -catalyzed process. [27] Thus both the high regioselectivity and the rate acceleration are accounted for by this mechanism. Similar results are obtained when calculating the Cu I -catalyzed cycloaddition reaction of azides to nitrile-oxides, for which a similar rate enhancement of the copper-catalyzed reaction in comparison to the purely thermal reaction was observed.…”

Section: Reviewmentioning

confidence: 99%

‘Click’ Chemistry in Polymer and Materials Science

Binder

Sachsenhofer

2007

Macromol. Rapid Commun.

1,480

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IntroductionThe azide/alkyne 'click' reaction [1] (also termed the Sharpless 'click' reaction) is a recent re-discovery of a reaction fulfilling many requirements for the affixation of ligands onto polymers by post-modification processes, which include a) often quantitative yields, b) a high tolerance of functional groups, c) an insensitivity of the reaction to solvents, irrespective of their protic/aprotic or polar/ non-polar character, and d) reactions at various types of interfaces, such as solid/liquid, liquid/liquid, or even solid/ solid interfaces. The present review focuses on issues related to the reaction itself as well as on the wide applications in polymer science, material, and surface science.The basic reaction, which is nowadays summed up under the name 'Sharpless-type click reaction', is a variant of the Huisgen 1,3-dipolar cycloaddition reaction [2a,2b] between C-C triple, C-N triple bonds, and alkyl-/aryl-/ sulfonyl azides (see Scheme 1).The relevant outcomes of this reaction are tetrazoles, 1,2,3-triazoles, or 1,2-oxazoles (Scheme 1a-c, respectively). Besides the 1,3-dipolar cycloaddition reaction, classical Diels-Alder-type reactions (Scheme 1d) have been used extensively for the functionalization of polymeric materials and surfaces. [3] These reactions are located within a series of reactions named click reactions, which is defined by a gain of thermodynamic enthalpy of at least 20 kcal Á mol À1 , [1] thus leading to reactions characterized by high yields, simple reaction conditions, fast reaction times, and high selectivity. Among many reactions tested, the 1,3-dipolar cycloaddition process has emerged as the method of choice to effect the requirements of ligating two ReviewThe modification of polymers after the successful achievement of a polymerization process represents an important task in macromolecular science. Cycloaddition reactions, among them the metal catalyzed azide/alkyne 'click' reaction (a variation of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides) represents an important contribution towards this endeavor. They combine high efficiency (usually above 95%) with a high tolerance of functional groups and solvents, as well as moderate reaction temperatures (25-70 8C). The present review assembles recent literature for applications of this reaction in the field of polymer science (linear polymers, dendrimers, gels) as well as the use of this and related reactions for surface modification on carbon nanotubes, fullerenes, and on solid substrates, and includes the authors own publications in this field. A number of references (>100) are included.

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“…This means that the difference in transition-state energy is about one third of the computed energy difference between the promoted complexes. Given that in our previous studies of arylnitrilimines [34] and arylazides [37] the regression slope was always 1, we checked whether the neglected constant electron potential term DW m (charge reshuffling) could counter-balance the constant external potential term DW of Equation (3) and reduce the slope. To this end, we computed the grand-potential contribution of the step at constant electron chemical potential as…”

Section: Resultsmentioning

confidence: 99%

“…This method has been successfully applied by us to the 1,3-DC between nitrilimines and alkynyl or alkenyl dipolarophiles, [34][35][36] and between arylazides and methyl propiolate. [37] Some qualitative predictions of the regiochemistry of the 1,3-DCs of nitrile oxides to electron-deficient acetylenes, based on DFT calculations, have been reported. [38] In order to have a clearer and more systematic picture of the substituent effect on the regioselectivity of the 1,3-DC of nitrile oxides to methyl propiolate, we present here a quantitative study of the regioselectivity observed in the cycloadditions between (4-substituted)benzonitrile oxides and methyl propiolate (see Scheme 1).…”

mentioning

confidence: 99%

DFT‐HSAB Prediction of Regioselectivity in 1,3‐Dipolar Cycloadditions: Behavior of (4‐Substituted)benzonitrile Oxides towards Methyl Propiolate

Ponti

Molteni

2006

Chemistry A European J

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The regioselectivity of 1,3-dipolar cycloadditions between (4-substituted)benzonitrile oxides and methyl propiolate cannot be rationalized on the basis of the electron demand of the reactants or frontier molecular-orbital theory. To this problem, we have applied a quantitative formulation of the hard-soft acid-base principle developed within the density functional theory. Global and local reactivity indices were computed at B3LYP/6-311+G(d,p) level. The details of charge transfer upon the reactive encounter have been elucidated, and the computed regioselectivity has been shown to be in good agreement with experimental data.

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Arylazide Cycloaddition to Methyl Propiolate: DFT‐Based Quantitative Prediction of Regioselectivity

Cited by 64 publications

References 47 publications

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

‘Click’ Chemistry in Polymer and Materials Science

DFT‐HSAB Prediction of Regioselectivity in 1,3‐Dipolar Cycloadditions: Behavior of (4‐Substituted)benzonitrile Oxides towards Methyl Propiolate

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