96475-94-4Relevant academic research and scientific papers
Regio- and Stereo-chemical Control in the Nickel-catalysed Addition of HCN to Alkynes. A Simple Synthesis of (E)-2-Alkyl-3-trialkylsilylalk-2-enenitriles
Fallon, Gary D.,Fitzmaurice, Neil J.,Jackson, W. Roy,Perlmutter, Patrick
, p. 4 - 5 (1985)
By varying the steric bulk of silicon substituents attached to alk-1-ynes it is possible to control, to a high degree, the regiochemical outcome of nickel(0)-catalysed hydrocyanations of alk-1-ynes: the crystal structure of one adduct is included which es
Palladium- and Nickel-Catalyzed Reaction of Trimethylsilyl Cyanide with Acetylenes. Addition of Trimethylsilyl Cyanide to the Carbon-Carbon Triple Bonds
Chatani, Naoto,Takeyasu, Takumi,Horiuchi, Nobuhiko,Hanafusa, Terukiyo
, p. 3539 - 3548 (2007/10/02)
The reaction of trimethylsilyl cyanide (1) with acetylenes in the presence of a transition-metal complex was investigated.The structures of starting acetylenes and catalysts and both amounts of solvent and 1 highly affected product distributions.The PdCl2/pyridine catalyzed reaction of phenylacetylene and para-substituted phenylacetylenes with 1 resulted in the addition of 1 to the carbon-carbon triple bonds to give cyano-substituted vinylsilanes in good to high yields with high regio- and stereoselectivity.Ortho-substituted phenylacetylenes gave addition products less stereoselectively.Stereoselectivity affording Z adducts decreased in the order of para- meta- ortho-substituted phenylacetylenes.The NiCl2/DIBAH-catalyzed reaction of arylacetylenes was less stereoselective regardless of substitution patterns of arylacetylenes used.When the nickel-catalyzed reaction of arylacetylenes was run without solvent using an excess amount of 1, 5-amino-1H-pyrrole-2-carbonitriles were obtained as a single product, instead of the above simple addition products.The reaction of terminal aliphatic acetylenes with 1 also gave addition products with moderate stereoselectivity.Internal acetylenes gave complex mixtures including addition products and/or pyrrole derivatives.Diarylacetylenes afforded 5-amino-1H-pyrrole-2-carbonitriles selectively in the presence of a palladium or nickel catalyst (without solvent and an excess amount of 1).Intramolecular cyclization of a 1,6-diyne was also studied.
THE STEREOCHEMISTRY OF ORGANOMETALLIC COMPOUNDS. XXXVI. REGIO- AND STEREO-CHEMICAL CONTROL IN THE NICKEL-CATALYSED HYDROCYANATION OF SILYLALKYNES
Fitzmaurice, Neil J.,Jackson, W. Roy,Perlmutter, Patrick
, p. 375 - 382 (2007/10/02)
The regioselectivity of hydrocyanation of silylalkynes can be controlled by varying the size of the groups attached to silicon leading, for example, to efficient preparations of E-3-trialkylsilyl-2-alkyl-2-alkenenitriles.High yields of the silylalkene nitriles can be obtained by using either acetone cyanohydrin or hydrogen cyanide as reagents.
