Me groups adjacent to an olefinic double bond were metalated by KOCMe3 and BuLi without cis-trans isomerization. Thus, (E)-MeCH:-CHMe was metalated to give (E)-MeCH:CHCH2K (I) which reacted with ethylene oxide to give 41% (E)-MeCH:CH(CH2)3OH. If I was allowed to equilibrate, the Z-isomer predominated (>99:1). Longer-chain olefins were metalated more slowly, with side reactions taking place. Thus, metalation of BuCH:CMe2 with EtCHMeBu and KOCMe3, followed by reaction with MeI gave 45% (Z)-BuCH:CMeEt, 9% BuCHMeCMe:CH2, and 19% Me(CH2)4CEt:CH2. [on SciFinder (R)]
Titre
Konfigurativ einheitliche Folgeprodukte aus Alkenylkalium-Zwischenstufen
Publié dans
Helvetica Chimica Acta
Volume
57
Numéro
6
Pages
1567-76
Date
1974
ISSN
0018-019X
Note
CAN 82:72486
23-2
Aliphatic Compounds
Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz.
Journal
written in German.
865-47-4 Role: RCT (Reactant), RACT (Reactant or reagent) (metalation by, of olefins); 590-18-1; 624-64-6; 4050-45-7; 7688-21-3 Role: RCT (Reactant), RACT (Reactant or reagent) (metalation of); 627-97-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and metalation of); 928-91-6P; 928-92-7P; 15870-10-7P; 31502-21-3P; 34213-99-5P; 34214-00-1P; 51174-44-8P; 54393-34-9P; 54393-35-0P; 54393-36-1P; 54393-37-2P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 693-03-8; 927-77-5 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with alkenyl esters); 74-88-4 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with alkenylpotassium compds.); 820-71-3 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with butylmagnesium bromide); 21406-61-1 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with ketones); 1779-49-3 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with methylheptanone); 106-68-3; 2371-19-9 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with methyltriphenylphosphonium bromide); 1191-16-8 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with propylmagnesium bromide); 75-21-8 Role: RCT (Reactant), RACT (Reactant or reagent) (with alkenylpotassium compds.); 78-93-3 Role: RCT (Reactant), RACT (Reactant or reagent) (with pentyltriphenylphosphonium bromide)
Date de création de la notice
2006-03-03
