Quantitative substituent effects in the Grignard reaction with silanes

Golubev, O. L.; Panov, Dmitri; Ploom, Anu; Tuulmets, Ants; Nguyen, Binh T.

doi:10.1016/j.jorganchem.2007.05.009

Cited by 8 publications

(11 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…7,8,15,16 It turned out that the well-known Taft equation (Equation 1) implicating terms for inductive (r*s*) and steric (dE S ) effects, differently of carbon compounds, cannot be applied for organosilicon compounds.…”

Section: Scheme 2 Mechanism Of the Grignard Reaction With Alkoxysilanesmentioning

confidence: 99%

Selectivity in the Grignard Reaction with Silanes

Tuulmets¹,

Ploom²,

Panov³

et al. 2010

Synlett

Self Cite

View full text Add to dashboard Cite

Selectivity problems in preparation of silanes by Grignard reaction were discussed. A quantitative approach in terms of LFE analysis was proposed. It appeared that the inductive effect controls the rate of replacement more considerably than steric requirements in the transition state. Rates of subsequent substitution reactions at silicon decrease stepwise. Only with methylmagnesium halides are the subsequent steps faster.

show abstract

Section: Scheme 2 Mechanism Of the Grignard Reaction With Alkoxysilanesmentioning

confidence: 99%

Selectivity in the Grignard Reaction with Silanes

Tuulmets¹,

Ploom²,

Panov³

et al. 2010

Synlett

Self Cite

View full text Add to dashboard Cite

show abstract

“…However, our attempts to calculate steric parameters for polar substituents failed entirely [20]. The values obtained for E S (Si) parameters varied by several times in case of different reaction series.…”

Section: Introductionmentioning

confidence: 97%

“…A linear correlation with purely inductive r o or r I constants rules out the conjugation of substituents with the reaction center [2]. Good correlations obtained for ten available reaction series [20] provided an evidence of insignificance of the resonance effect at least in nucleophilic displacement reactions at the silicon center. From the brief analysis above it follows that a revision of quantitative literature data for the reactivity of organosilicon compounds in light of current conceptions is necessary.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A novel insight into the inductive effect in silicon chemistry

Ploom

Tuulmets

2009

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

“…However, despite of the technological significance of this reaction, its mechanism and especially the quantitative aspects of organosilane formation have not well understood. Proceeding from this fact we have launched an extensive program of kinetic investigation of this reaction, focussing incidentally on the influence of Grignard reagent solvation on its reactivity [2][3][4][5][6]. Besides theoretical interest, this latter aspect was strongly motivated by practical needs, emerging from technological application of the Grignard reaction under conditions, where ether solvents are replaced by hydrocarbons of higher boiling points to meet the safety requirements of this technology.…”

Section: Introductionmentioning

confidence: 99%