74796-60-4Relevant academic research and scientific papers
Three Coordinated Organoaluminum Cation for Rapid and Selective Cyanosilylation of Carbonyls under Solvent-Free Conditions
Bhandari, Mamta,Prashanth, Billa,Rawat, Sandeep,Singh, Sanjay
, (2020)
The well-defined three coordinated electronically unsaturated cationic organoaluminum complex [({(2,6-iPr2C6H3N)P(Ph2)}2N)AlMe]+[MeB(C6F5)3]? (1), has been utilized to catalyze the cyanosilylation of aldehydes and ketones under mild and solvent-free conditions. Moreover, catalyst 1 showed high chemoselective cyanosilylation of aldehydes over ketones, nitriles and olefins. The multinuclear NMR investigations revealed that cyanosilylation proceeds via Lewis adduct formation between 1 and TMSCN thereby activating TMSCN (Si-CN bond) followed by nucleophilic attack of the carbonyl oxygen at the Si center of the activated silane and formation of the product.
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.
A SIMPLE ROUTE TO Δ2-BUTENOLIDES FROM CONJUGATED ALDEHYDES
Corey, E. J.,Schmidt, Greg
, p. 731 - 734 (2007/10/02)
A variety of Δ2-butenolides may be synthesized by oxidation of the O-trimethylsilylcyanohydrins of α,β-unsaturated aldehydes using pyridinium dichromate in dimethylformamide.
