The origin of exo-stereoselectivity of norbornene in hetero Diels–Alder reactions

Çınar, Sesil Agopcan; Ercan, Selami; Gunal, Sule Erol; Doğan, İlknur; Avi̇yente, Vi̇ktorya

doi:10.1039/c4ob01217h

Cited by 14 publications

(3 citation statements)

References 69 publications

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“…This has been validated computationally, as the endo transition state is approximately 2 kcal mol −1 higher in energy than the exo transition state owing to high electrostatic repulsive forces . Another example of exo selectivity is the reaction of thione 21 with norbornene ( 22 ) (Figure b), and the selectivity is attributed to large distortions in norbornene and an eclipsed conformation of the transition state …”

Section: Mechanistic Studies Of the Iedda Reactionmentioning

confidence: 83%

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Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Png

Zeng

et al. 2017

Chemistry An Asian Journal

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Inverse-electron-demand Diels-Alder (iEDDA) reactions are an intriguing class of cycloaddition reactions that have attracted increasing attention for their application in bioorthogonal chemistry, the total synthesis of natural products, and materials science. In many cases, the application of the iEDDA reaction has been demonstrated as an innovative approach to achieve target structures. The theoretical aspects of this class of reactions are of particular interest for scientists as a means to understand the various factors, such as steric strain and electron density of the attached groups, that govern the reaction and thus to elucidate the reaction mechanism. This review aims to summarize both theoretical investigations and application-driven research work on the iEDDA reaction. First, the historical aspects and the theoretical basis of the reaction, especially recent advances in time-dependent density functional theory (TD-DFT) calculations, as well as catalysis strategies will be highlighted and discussed. Second, the applications of this novel reaction in the context of materials science, bioorthogonal chemistry, and total synthesis of natural products will be elaborated with selected recent examples. The challenges and opportunities of the iEDDA reaction will be highlighted to give more insight into its potential applications in many other research areas.

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Section: Mechanistic Studies Of the Iedda Reactionmentioning

confidence: 83%

“…[20] Another example of exo selectivity is the reaction of thione 21 with norbornene (22) ( Figure 3b), and the selectivity is attributedt ol arge distortions in norbornene and an eclipsed conformationo ft he transition state. [21]…”

Section: Endo/exo Selectivitymentioning

confidence: 99%

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Png

Zeng

et al. 2017

Chemistry An Asian Journal

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“…Conveniently, there is no special computer code required to perform activation strain analyses: all necessary quantities can be computed using any of the regular quantum‐chemical software packages available. As a result, the activation strain model has been applied by various research groups, on a range of chemical processes, such as nucleophilic substitution, cycloaddition, oxidative addition, isomerization, and many other processes from organic and organometallic chemistry.…”

Section: Introductionmentioning

confidence: 99%

The activation strain model and molecular orbital theory

Wolters

Bickelhaupt

2015

WIREs Comput Mol Sci

304

229

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The activation strain model is a powerful tool for understanding reactivity, or inertness, of molecular species. This is done by relating the relative energy of a molecular complex along the reaction energy profile to the structural rigidity of the reactants and the strength of their mutual interactions: ΔE(ζ) = ΔEstrain(ζ) + ΔEint(ζ). We provide a detailed discussion of the model, and elaborate on its strong connection with molecular orbital theory. Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms. This methodology may reveal intriguing parallels between completely different types of chemical transformations. Thus, the activation strain model constitutes a unifying framework that furthers the development of cross-disciplinary concepts throughout various fields of chemistry. We illustrate the activation strain model in action with selected examples from literature. These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process. WIREs Comput Mol Sci 2015, 5:324–343. doi: 10.1002/wcms.1221

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Formation of Active Cyclic Five‐membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions

Dong

Daniliuc

Kehr

et al. 2019

Chemistry A European J

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The cyclic five-membered frustratedp hosphane/ borane Lewis pairs 11 a, b featuring the bulky octaethylhydrindacenyl-(Eind) substituento ri ts mono-bromod erivative ( Br Eind)a tp hosphorus are monomeric at room temperature. The reactive frustrated Lewis pairs (FLPs) cleave dihydrogen. The cyclic FLP 11 b ( Br Eind) undergoes 1,2-P/B addition to ethylene to give the zwitterionic heteronorbornane derivative 14 b.I tr eacts similarly with the carbon-carbon double bond of norbornene.W ith av ariety of organic p-reagents, the cyclic FLP 11 b often undergoes reaction sequences reminiscent of the Alder-Rickert reaction:the cycloaddition reaction is followed by rapid cycloreversion to form new fivemembered heterocyclic FLP products with extrusion of ethene. Reactions of 11 b with benzaldehydeo rw ith acetylenesf ollow this reactionpattern.Scheme1.Previously reported P/B cyclo-FLPs and the bulkyaryl ligands used in this study.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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The origin of exo-stereoselectivity of norbornene in hetero Diels–Alder reactions

Cited by 14 publications

References 69 publications

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

Inverse‐Electron‐Demand Diels–Alder Reactions: Principles and Applications

The activation strain model and molecular orbital theory

Formation of Active Cyclic Five‐membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions

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