59738-55-5Relevant academic research and scientific papers
Catalytic activation of silylated nucleophiles using tBu-P4 as a base
Ueno, Masahiro,Hori, Chieko,Suzawa, Koichi,Ebisawa, Masashi,Kondo, Yoshinori
, p. 1965 - 1968 (2005)
Trialkylsilyl groups play an important role as effective protecting groups in organic synthesis. Various O, N, and C nucleophilic sites can be protected by trialkylsilyl groups to control the selectivity of reactions. The nucleophilic attack of a fluoride anion on a silyl group is recognized as one of the most useful methods for desilylation. The activation of the nucleophile-silicon bond is important not only for desilylation but also for the generation of a reactive nucleophilic anion to achieve a new bond formation. The phosphazene bases developed by Schwesinger are known to be strong non-metallic organic bases. Among them, the tBu-P4 base has been used for various selective deprotonative transformations, although the ability of tBu-P4 base to activate silylated nucleophiles has not yet been shown. A novel catalytic activation of various O, N, and C nucleophile-silicon bonds using tBu-P4 base was investigated to perform nucleophilic reactions with various electrophiles. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Trimethylsilylphenylacetylene in C-Alkynylation Reactions
Komissarova,Aleksandrova,Stadnichuk
, p. 412 - 416 (2007/10/03)
Direction and yields of products of the reaction between phenylethynyl anions, generated from trimethylsilylphenylacetylene under the action of potassium fluoride in DMF, and C-electrophilic reagents (aliphatic and aromatic aldehydes and ketones, aliphatic and aromatic acyl chlorides, aryl halides, and alkenyl chlorides with chlorine in the allylic position) are controlled by their structure. Secondary acetylenic alcohols prepared from aromatic aldehydes, as well as their trimethylsilyl ethers, undergo uncatalyzed Meyer-Schuster rearrengement.
FLUORIDE CATALYZED REACTION OF SILYLACETYLENES WITH CARBONYL COMPOUNDS
Kuwajima, I.,Nakamura, E.,Hashimoto, K.
, p. 975 - 982 (2007/10/02)
(Phenylethynyl)trimethylsilane undergoes nucleophilic addition to a variety of carbonyl compounds in the presence of a catalytic amount of fluoride anion to give silylated propargyl alcohol derivatives.The reaction fails with enolizable enones and cyclopentanone.The reaction of bis(trimethylsilyl)acetylene does not stop at the stage of monoadduct, and affords a considerable amount of symmetric bisadduct. (Trimethylsilyl)acetylene attacks 4-t-butylcyclohexanone from the axial side, as other metal acetylides do.Although much slower than the above cases, the reaction of alkynyltrimethylsilanes also proved successful.The reactivities of these (trimethylsilyl)-acetylenes are discussed in terms of the reaction mechanism and the nature of the reactive species, and also compared with those of the silylated enols under similar conditions.
