pi-Arene/Metal Binding: An Issue Not Only of Structure but Also of Reactivity

A trimethyl-, triethyl-, or triisopropylsilyl group attached to the meta position of toluene retards the rate of permutational H/metal interconversion with butyllithium in the presence of K tert-butoxide by factors of 1.7, 3, and 7, resp. Although remote from the reaction center, the substituents sterically impede the coordination of K to the arene electron sextet. p-Arene/metal bonding may play a major role in modulating chem. and, by extension, biochem. reactivity. [on SciFinder (R)]


Published in:
Organic Letters, 7, 10, 1923-1925
Year:
2005
Keywords:
Note:
CAN 143:26664 29-6 Organometallic and Organometalloidal Compounds Institute of Chemical Sciences and Engineering (ISIC),Ecole Polytechnique Federale,Lausanne,Switz. Journal 1523-7060 written in English. 3644-91-5; 3728-43-6; 3728-44-7; 7450-03-5; 17897-63-1; 18412-77-6; 18412-78-7 Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (p-arene/metal bonding and substituent effects on metalation kinetics of trialkyl(tolyl)silanes with BuLi in presence of potassium tert-butoxide); 994-30-9 (Chlorotriethylsilane); 1611-92-3 (3,5-Dibromotoluene) Role: RCT (Reactant), RACT (Reactant or reagent) (p-arene/metal bonding and substituent effects on metalation kinetics of trialkyl(tolyl)silanes with BuLi in presence of potassium tert-butoxide); 852872-17-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (p-arene/metal bonding and substituent effects on metalation kinetics of trialkyl(tolyl)silanes with BuLi in presence of potassium tert-butoxide); 18414-83-0P; 18415-19-5P; 852872-18-5P; 852872-19-6P Role: SPN (Synthetic preparation), PREP (Preparation) (p-arene/metal bonding and substituent effects on metalation kinetics of trialkyl(tolyl)silanes with BuLi in presence of potassium tert-butoxide); 7440-09-7 (Potassium) Role: PRP (Properties) (p-arene/metal interaction of; p-arene/metal bonding and substituent effects on metalation kinetics of trialkyl(tolyl)silanes with BuLi in presence of potassium tert-butoxide)
Other identifiers:
Laboratories:




 Record created 2006-03-03, last modified 2018-01-27


Rate this document:

Rate this document:
1
2
3
 
(Not yet reviewed)