Estimation of the pKa for Some Hydrocarbons and Aldehydes and Solvation Energies of the Corresponding Anions.

Daasbjerg, Kim; Oslob, Johan D.; Norrby, Per-Ola

doi:10.3891/acta.chem.scand.49-0878

Cited by 24 publications

(19 citation statements)

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“…As we have discussed in a preliminary report, trajectories at a lower temperature gave a higher propensity towards an ET process for reaction (3). 7c A similar trend was found in the present study for reaction (2), which according to path-following calculations belongs to a borderline case. For this system, all trajectories that went to the product state at 298 K were of the ET type.…”

Section: Hc(cn)=osupporting

confidence: 91%

“…All three TS structures have characteristics of S N 2 reactions, with the asymmetric motion of the C-C-Cl unit dominating the reaction coordinate. The TS for reaction (2) is looser than that for reaction (1) and the C-C-Cl angle differs from 180°o wing to steric effects. The TS for reaction (3) is more reactant-like than that for reaction (1), in accord with Hammond's postulate.…”

Section: Mo Calculationsmentioning

confidence: 86%

“…Thus the ET process in the borderline reaction has similar characteristics to the process of a pure ET mechanism. One difference is that the electron reorganization is sharper here in reaction (3) than in ET reaction (2). This difference may be related to the tighter TS and hence to the stronger interaction between the fragments in reaction (3) compared with reaction (2).…”

Section: Hc(cn)=omentioning

confidence: 92%

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Ab initio molecular dynamics studies on substitution vs electron transfer reactions of substituted ketyl radical anions with chloroalkanes: how do the two products form in a borderline mechanism?

Yamataka

Aida

Dupuis

2003

J of Physical Organic Chem

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We present a qualitative analysis, based on ab initio molecular dynamics (MD) calculations, of the S N 2/ ET mechanistic spectrum for three reactions: (1) HC(CN)=O . À CH 3 Cl, (2) HC(CN)=O . À (CH 3 ) 2 CHCl and (3) H 2 C=O . À CH 3 Cl, passing through their S N 2-like transition states. Finite temperature (298 K) direct MD simulations indicate that the trajectories for reaction (1) appear to have a propensity towards S N 2 products, the propensity for trajectories for reaction (2) seems to be towards ET products, whereas trajectories for reaction (3) appear to show no particular propensity towards either ET or S N 2 products. The mechanistic diversity is consistent with the electron-donating ability of the ketyl species and steric bulkiness of chloroalkanes. We find that the trajectories have characteristics that reflect strongly the types of process [S N 2 trajectories in reactions (1) and (3) vs ET trajectories in reactions (2) and (3)]. Trajectories that lead to S N 2 products are simple with C-C bond formation and C-Cl bond breaking essentially completed within 50 fs. By contrast, trajectories leading to ET products are more complex with a sudden electron reorganization taking place within 15-30 fs and the major bonding changes and electron and spin reorganizations completed after 250 fs.

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Section: Hc(cn)=osupporting

confidence: 91%

Section: Mo Calculationsmentioning

confidence: 86%

Section: Hc(cn)=omentioning

confidence: 92%

See 1 more Smart Citation

Ab initio molecular dynamics studies on substitution vs electron transfer reactions of substituted ketyl radical anions with chloroalkanes: how do the two products form in a borderline mechanism?

Yamataka

Aida

Dupuis

2003

J of Physical Organic Chem

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“…The basicity of CÀHb onds decreases in the following order:e thane > ethene > propyne > ethyne with pK a values of 62, 45, 38 and 26, respectively. [23] Accordingly,t he ethyl Grignardr eagent should be the most reactive, but the difference in basicityb etween the ethyl and vinyl groups in the reaction is negligible (note that these very high pK a values are very difficult to measure, with estimated errors of ca. 5u nits).…”

Section: Resultsmentioning

confidence: 99%

Fluorographene Modified by Grignard Reagents: A Broad Range of Functional Nanomaterials

Mazánek

Libánská

Šturala

et al. 2017

Chemistry A European J

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Fluorographene is the youngest stoichiometric derivative of graphene; hence, its reactivity is only poorly explored. Compared to graphene, the significantly higher reactivity of C-F bonds makes this material a suitable platform for a large number of chemical modifications. Fluorographene is also the only member of the halographene family that can be prepared in the stoichiometric composition (C F ). Herein, the chemical modification of fluorographene with Grignard reagents, which are well known in organic synthesis for the formation of new C-C bonds, is presented. The reaction with alkyl magnesium bromides led to successful modification of fluorographene with ethyl, vinyl, ethynyl and propargyl groups. Chemical characterisation showed the presence of covalently bonded functional groups in a high concentration exceeding one functional group per C motif. The reactivity of Grignard reagents with fluorographene decreased from ethyl to ethynyl. The terminal carbon-carbon triple bonds were used for click reactions with organic azides leading to the formation of triazole rings. These findings open up a broad spectrum of opportunities for simple and robust modification of graphene by chemical reactions proceeding at room temperature under mild conditions. These results have major application potential in sensing, biomedical and energy-related applications.

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“…Zuschriften lithium (pK a 51 [11] ), reacted nucleophilically with the amide to form, for example, 2-hydroxyphenyl-sec-butylketone (Entry 9). Reactions with potassium hexamethyldisilazide (KHMDS, pK a 29.5 [9] ) and NaH did not afford the desired product (Entries 8 and 6, respectively).…”

Section: Methodsmentioning

confidence: 99%

ChemInform Abstract: Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone.

Lin

Tseng

et al. 2015

ChemInform

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Lithiation of a Silyl Ether: Formation of an ortho-Fries Hydroxyketone. -Ortho-hydroxy amides are alkylated by LDA and chlorosilanes. This method is also applied to an anionic Snieckus-Fries rearrangement. The synthesis of PI3K inhibitor (XIV) can be also accomplished by using this rearrangement reaction as key step. -(LO, H.-J.; LIN, C.-Y.; TSENG, M.-C.; CHEIN*, R.-J.; Angew. Chem., Int. Ed. 53 (2014) 34, 9026-9029, http://dx.

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Estimation of the pKa for Some Hydrocarbons and Aldehydes and Solvation Energies of the Corresponding Anions.

Cited by 24 publications

References 0 publications

Ab initio molecular dynamics studies on substitution vs electron transfer reactions of substituted ketyl radical anions with chloroalkanes: how do the two products form in a borderline mechanism?

Ab initio molecular dynamics studies on substitution vs electron transfer reactions of substituted ketyl radical anions with chloroalkanes: how do the two products form in a borderline mechanism?

Fluorographene Modified by Grignard Reagents: A Broad Range of Functional Nanomaterials

ChemInform Abstract: Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone.

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