99337-14-1

Upstream product

• 7677-24-9 trimethylsilyl cyanide 
• 536-74-3 phenylacetylene 
• 2170-06-1 1-Phenyl-2-(trimethylsilyl)acetylene 

Downstream Products

• 99337-21-0 2-phenyl-3-(trimethylsilyl)propanenitrile 

Relevant academic research and scientific papers

Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1-Methylcyclohexa-2,5-diene-1-carbonitrile

Catalytic transfer hydrocyanation represents a clean and safe alternative to hydrocyanation processes using toxic HCN gas. Such reactions provide access to pharmaceutically important nitrile derivatives starting with alkenes and alkynes. Herein, an efficient and practical cooperative palladium/Lewis acid-catalyzed transfer hydrocyanation of alkenes and alkynes is presented using 1-methylcyclohexa-2,5-diene-1-carbonitrile as a benign and readily available HCN source. A large set of nitrile derivatives (>50 examples) are prepared from both aliphatic and aromatic alkenes with good to excellent anti-Markovnikov selectivity. A range of aliphatic alkenes engage in selective hydrocyanation to provide the corresponding nitriles. The introduced method is useful for chain walking hydrocyanation of internal alkenes to afford terminal nitriles in good regioselectivities. This protocol is also applicable to late-stage modification of bioactive molecules.

Palladium- and Nickel-Catalyzed Reaction of Trimethylsilyl Cyanide with Acetylenes. Addition of Trimethylsilyl Cyanide to the Carbon-Carbon Triple Bonds

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.

SYNTHESIS OF 5-AMINO-2-CYANO-4-SILYLPYRROLES FROM SILYLACETYLENES AND TRIMETHYLSILYL CYANIDE

The reaction of silylacetylenes with trimethylsilyl cyanide in the presence of palladium catalysts gives 3-substituted 5-(N,N-bis(trimethylsilyl)amino)-2-cyano-4-silylpyrroles with high regioselectivity.

Palladium-catalysed Addition of trimethylsilyl Cyanide to Arylacetylenes

The reaction of arylacetylenes with trimethylsilyl cyanide (1) in the presence of a palladium complex resulted in addition of (1) across the carbon-carbon triple bond with high regio- and stereo-selectivity to give β-cyano-β-arylalkenylsilanes.