135664-53-8

Upstream product

• 24214-79-7 cyclohexanone benzoylhydrazone 
• 143-33-9 sodium cyanide 
• 1360557-39-6 1-(phenylsulfinyl)cyclohexanecarbonitrile 
• 98-88-4 benzoyl chloride 
• 93-89-0 benzoic acid ethyl ester 
• 5222-53-7 cyclohexane-1,1-dicarbonitrile 
• 98-80-6 phenylboronic acid 
• 712-50-5 Cyclohexyl phenyl ketone 
• 7500-66-5 (1-bromocyclohexyl)(phenyl)methanone 
• 55305-43-6 N-cyano-N-phenyl-p-toluenesulfonamide 
• 27702-92-7 1-(1-cyanocyclohexyl)-2-benzoyldiazene 

Relevant academic research and scientific papers

Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles

β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.

Access to α-Cyano Carbonyls Bearing a Quaternary Carbon Center by Reductive Cyanation

Reductive cyanation of tertiary alkyl bromides using electrophilic cyanating reagent and zinc reductant was developed, providing various α-cyano ketones, esters, and carboxamides containing a nitrile-bearing all-carbon quaternary center in good to excellent yields under mild reaction conditions. The corresponding reaction mechanism involving in situ generated organozinc reagent and reactivity distinction was elucidated by density functional theory computation.

Electrophilic Cyanation of Boron Enolates: Efficient Access to Various β-Ketonitrile Derivatives

The highly efficient electrophilic cyanation of boron enolates using readily available cyanating reagents, N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) and p-toluenesulfonyl cyanide (TsCN), is reported. Various β-ketonitriles were prepared by this new protocol, which has a remarkably broad substrate scope compared to existing methods. The present method also allowed efficient synthesis of β-ketonitriles containing a quaternary α-carbon center. In addition, a preliminary result with the use of a chiral boron enolate for the enantioselective cyanation reaction is described.

Chemoselective Alkylations with N- and C-Metalated Nitriles

Metalated nitriles exhibit complementary chemoselectivities in electrophilic alkylations. N-Lithiated or C-magnesiated nitriles can be prepared from the same nitrile precursor and selectively reacted with a 1:1 mixture of methyl cyanoformate and benzyl br

Phase-Transfer Catalyzed Formation of α-Cyano Ketones from Ketone Aroylhydrazones in NaCN(aq)-Inert Organic Solvent System

α-Cyanoalkyl aryl ketones can be obtained from ketone aroylhydrazones by heterogeneous reaction with aqueous sodium cyanide, an inert organic solvent, and acetic acid in the presence of air and a catalytic amount of a quaternary ammonium salt.The initiall