In the blind spot of diffusion control: 2-fluoroallyl cations and their various possibilities for stabilization
Three new model substrates of the chlorofluorocyclopropane type (I, II, and III) were submitted to silver ion-assisted ring opening. No rearrangement, but only fragmentation or direct solvolysis, occurred. In the latter case, primary rather than tertiary 2-fluoroallyl alcs. were formed almost exclusively. Nucleophilic attack at the unsubstituted terminus of the 2-fluoroallyl cation was apparently favored for steric reasons. [on SciFinder (R)]
Keywords: Regiochemistry (of fluoroallyl carbocation reactions in spirocyclic chlorofluorocyclopropane solvolysis); Solvolysis (of spirocyclic chlorofluorocyclopropanes in presence of silver ion ; regiochem. of fluoroallylcarbocation reaction in); Ring cleavage (o ; cyclopropane chlorofluoro ring cleavage silver; ring cleavage chlorofluorocyclopropane silver; spirocyclic chlorofluorocyclopropane solvolysis silver; fluoroallyl carbocation stabilization; steric effect fluoroallyl carbocation reaction; regiochem fluor
Physical Organic Chemistry
Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz.
written in English.
79-92-5 (Camphene); 127-91-3 (b-Pinene); 471-84-1 (a-Fenchene) Role: RCT (Reactant), RACT (Reactant or reagent) (carbene reaction of, with dichlorofluoromethane); 75-43-4 (Dichlorofluoromethane) Role: RCT (Reactant), RACT (Reactant or reagent) (carbene reaction of, with olefins); 135655-04-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and hydrolysis of); 135654-99-8P; 135655-00-4P; 135655-01-5P; 135684-70-7P; 135911-36-3P; 135911-37-4P; 135911-38-5P; 135911-39-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and solvolytic ring cleavage of, in presence of silver ion); 91965-58-1P; 135655-02-6P; 135655-03-7P; 135655-05-9P; 135655-06-0P; 135655-07-1P; 135655-08-2P; 135655-09-3P; 135655-10-6P; 135655-11-7P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of)
Record created on 2006-03-03, modified on 2016-08-08