100573-48-6Relevant articles and documents
Trimethylsilyl Cyanide - A Reagent for Umpolung, XI. On the Ambident Character of Substituted Allylic Anions.
Huenig, Siegfried,Reichelt, Helmut
, p. 1772 - 1800 (2007/10/02)
The dependence of the α/γ-ratio of alkylation products on several factors has been determined with 1-cyano-3-aryl-1-(trimethylsiloxy)allylic anions.Increasing amounts of γ-product are found in more polar solvents, with larger alkali ions, on addition of HMPT, with smaller alkyl groups in the electrophile, and especially with p-cyanophenyl groups.In contrast, temperature and leaving groups have minor effects.On substitution of the O-silyl group by O-methyl and O-ethoxycarbonyl, α-alkylation predominates strongly.The results are compared to known allylic anions.Furthermore, the isomerisation of compounds of type C to type B is described as well as a new addition reaction of cyanoformates to aldehydes.