Computational study of carbon–hydrogen bond deprotonation by alkali metal superbases

Pardue, Daniel B.; Gustafson, Samantha J.; Periana, Roy A.; Ess, Daniel H.; Cundari, Thomas R.

doi:10.1016/j.comptc.2013.06.041

Cited by 22 publications

(19 citation statements)

References 65 publications

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“…To further examine the nucleophilic side of the CH activation continuum, the our group and the Cundari group undertook a computational study [59] of alkali metal amide and alkaline earth metal amide CH activation reactions with alkanes. This study is directly related to classic superbase chemistry using cesium cyclohexylamide-type reagents to induce CH bond deprotonation of alkanes [60].…”

Section: [(Hbpym)ptcl]mentioning

confidence: 99%

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

King

Gustafson

Ess

2015

Structure and Bonding

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Alkane CH activation is a fundamental reaction class where a metalligand complex reacts with a CH bond to give a metal-alkyl organometallic intermediate. CH activation reactions have been reported for a variety of transition metals and main-group metals. This chapter highlights recent quantum-mechanical studies that have used energy decomposition analysis (EDA) to provide insight into σ-coordination complexes and transition states for alkane CH activation reactions. These studies have provided new conceptual understanding of CH activation reactions and detailed insight into the physical nature and magnitude of interaction between alkanes with transition metals and main-group metals.

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Section: [(Hbpym)ptcl]mentioning

confidence: 99%

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

King

Gustafson

Ess

2015

Structure and Bonding

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“…We next explored the origin of the nitrogen atom in the indole by employing 15 15 Nf or 14 No ccurs via intermediates C, D,and E (Scheme 5). [28] Forthis to be true,transimination would need to be faster than S N Ar.…”

Section: Zuschriftenmentioning

confidence: 99%

“…Our team has been interested in the use of common feedstocks for the synthesis of value-added fine chemicals of pharmaceutical interest. Our strategy to facilitate the use of toluene derivatives relies on cation-p interactions [14] between Group Imetal cations and the p-system of toluene derivatives to acidify the benzylic hydrogen atoms (pK a % 43 [15] in DMSO) to the extent that they can be reversibly deprotonated with relatively mild MN(SiMe 3 ) 2 bases (HN(SiMe 3 ) 2 : pK a % 26 [16] in THF). As proof of concept (Scheme 2a), reactions of toluene derivatives with NaN(SiMe 3 ) 2 in the presence of Cs + salts initially resulted in the formation of the N-SiMe 3 imines.T he key finding was that under the reaction conditions (40-110 8 8C), toluene derivatives could be reversibly deprotonated.…”

mentioning

confidence: 99%

Synthesis of Indoles through Domino Reactions of 2‐Fluorotoluenes and Nitriles

Mao

Wang

et al. 2019

Angew Chem Int Ed

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Indoles are essential heterocycles in medicinal chemistry,a nd therefore,n ovel and efficient approaches to their synthesis are in high demand. Among indoles,2 -aryl indoles have been described as privileged scaffolds.Advanced herein is astraightforward, practical, and transition-metal-free assembly of 2-aryl indoles.Simply combining readily available 2-fluorotoluenes,n itriles,L iN(SiMe 3 ) 2 ,a nd CsF enables the generation of adiverse arrayofindoles (38 examples,48-92 % yield). Ar ange of substituents can be introduced into each position of the indole backbone (C4 to C7, and aryl groups at C2), providing handles for further elaboration. Scheme 1. Transition-metal-free synthesis of indoles.

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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

305

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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Computational study of carbon–hydrogen bond deprotonation by alkali metal superbases

Cited by 22 publications

References 65 publications

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

Synthesis of Indoles through Domino Reactions of 2‐Fluorotoluenes and Nitriles

The activation strain model and molecular orbital theory

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