Reaction of cis- and trans-PhCH:CHF with RLi (R = Bu, Me, Ph, or PhCH2) gave stereoselectively cis- and trans-PhCH:CHR, with retention of configuration by substitution and PhC.tplbond.CH by elimination reaction. The elimination reaction follows mainly the E2cb mechanism. The substitution reaction is accomplished by an addn.-elimination sequence with extremely short-lived intermediates. These mechanisms are based on isotope effect, B-ligand effect, and F/Cl elemental effect measurements. The enhanced reactivity of vinyl fluorides towards substitution might be caused by repulsive interactions of neighboring nonbonding p-electrons. [on SciFinder (R)]
Title
Reaktionen zwischen Vinylfluoriden und Lithiumorganylen
Published in
Chemische Berichte
Volume
104
Issue
9
Pages
2885-95
Date
1971
Note
CAN 75:140082 22 Physical Organic Chemistry Org.-Chem. Inst.,Univ. Heidelberg,Heidelberg,Fed. Rep. Ger. Journal 0009-2940 written in German. 7782-39-0 Role: PRP (Properties) (isotopic effect of, on butyllithium reaction with styryl fluoride); 34237-77-9P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 4110-77-4; 4604-28-8 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with butyllithium); 20405-77-0; 20405-78-1 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with organolithium compds.); 591-51-5; 766-04-1; 917-54-4 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with styryl fluoride); 109-72-8 Role: RCT (Reactant), RACT (Reactant or reagent) (with styryl halides, mechanism of)
Record creation date
2006-03-03
