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

Abstract

b-Ketonitriles bearing aquaternary carbon at the 2position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles.Incontrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles,t he present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of am ilder base.T he reaction was amenable to av ariety of aryl boronic acids and disubstituted malononitriles,providing adiverse array of b-ketonitriles.The products could be further derivatized to valuable chiral a,adisubstituted-b-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Biocatalytic Synthesis of Nitrile-Bearing All-Carbon Quaternary Stereocenters

“…α-Cyano carbonyl compounds are very important in the construction of bioactive molecules. − The presence of these motifs along with all-carbon quaternary stereocenters, which leads to an increase in the metabolic stability of pharmaceuticals, has long been an attractive topic, and significant progress has been made in the synthesis of α-cyano carbonyl compounds. ,− …”

Transition-metal-catalyst-free reaction of amides and acetonitriles: synthesis of β-ketonitriles

“…Various synthetic methods for accessing β-ketonitriles have been developed, including nucleophilic cyanation, 8 the ring opening of isoxazoles, 9 the electrophilic cyanation of enolates, 10 the umpolung acylation of aldehydes with 2-bromoacetonitrile, 11 the addition of aryl boronic acids to malononitrile, 12 the addition of diazoacetonitrile to aldehydes, 13 and the oxidative coupling of alcohols with acetonitrile. 14 Among them, palladium-catalyzed carbonylative coupling, electrophilic cyanation, and acyl substitution are the most commonly employed methods for the convenient preparation of β-ketonitriles (Scheme 1A-a).…”