1-(Triphenylmethyl)allylpotassium: conformational preference and [1,2]-rearrangement

• Published in: Tetrahedron, vol. 44, num. 12, p. 3539-50
• Publication date: 1988

Upon treatment with the superbasic 1:1 mixt. of BuLi and Me3COK, cis- and trans-1,1,1-triphenyl-2-butene as well as 4,4,4-triphenyl-1-butene undergo a hydrogen/metal exchange to afford 1-(triphenylmethyl)allylpotassium [4,4,4-triphenyl-2-butenylpotassium] which exists in two stereoisomeric forms. Torsional equilibration leads to an endo/exo ratio of approx. 50:50. Novel endo-stabilizing interactions are discussed to rationalize this result. At temps. around or above 0 Deg, a Ph 1,2-migration, though no 1,4-migration, takes place. [on SciFinder (R)]

Keywords: Rearrangement (of triphenylmethylallylpotassium) ; phenylmethylallylpotassium formation conformational preference rearrangement; rearrangement conformation triphenylmethylallylpotassium

Note:

CAN 111:7452

29-2

Organometallic and Organometalloidal Compounds

Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz.

Journal

0040-4020

written in English.

1530-32-1 (Ethyltriphenylphosphonium bromide) Role: RCT (Reactant), RACT (Reactant or reagent) (Wittig reaction by, of triphenylacetaldehyde); 106-95-6 (Allylbromide) Role: RCT (Reactant), RACT (Reactant or reagent) (allylation by, of triphenylmethane, triphenylbutene by); 519-73-3 (Triphenylmethane) Role: RCT (Reactant), RACT (Reactant or reagent) (allylation of, with allyl bromide, triphenylbutene by); 119297-15-3P; 119297-16-4P Role: RCT (Reactant), PREP (Preparation), RACT (Reactant or reagent) (formation and rearrangement of); 42365-04-8P (Triphenylacetaldehyde) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Wittig reaction of, with ethylenetriphenylphosphorane); 16876-20-3P (4,4,4-Triphenyl-1-butene) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and catalyzed isomerization of); 121136-58-1P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and hydrolysis of); 121136-50-3P; 121136-51-4P; 121136-54-7P; 121136-55-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and methylation of); 121136-48-9P; 121136-49-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and methylation of, conformation preference in relation to); 121136-52-5P; 121136-53-6P; 121136-56-9P; 121136-57-0P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of)

Reference

• LSCO-ARTICLE-1988-002
• doi:10.1016/S0040-4020(01)85984-6

Record created on 2006-03-03, modified on 2016-08-08