Synthesis of α‐Aryl Nitriles through Palladium‐Catalyzed Decarboxylative Coupling of Cyanoacetate Salts with Aryl Halides and Triflates

Photoredox Catalysis in Nickel-Catalyzed Cross-Coupling

“…Their use as nucleophilic partners in decarboxylative cross-couplings with aryl halides to form C(sp2)-C(sp2) bonds has been well established, and many examples with benzoic acid derivatives as well as aryl and heteroaryl halides have been reported to date [40,41]. Nonetheless, alkyl carboxylic acids are more challenging partners in crosscouplings reactions, often requiring activated substrates such as cyclohexadienyl [42] or a-cyano acids [43]. The pioneering work of MacMillan/Doyle and coworkers using the synergistic photoredox/nickel catalysis strategy for crosscoupling of a-amino acids is a viable alternative to the reported methods [44].…”

Cyanoacetic Acid as a Masked Electrophile: Transition‐Metal‐Free Cyanomethylation of Amines and Carboxylic Acids

“…Recently, Liu7a,c and Tunge7h,i et al. developed cyanomethylation reactions by decarboxylation of α ‐cyanoacetic acids and its derivatives 7.…”

“…developed cyanomethylation reactions by decarboxylation of α ‐cyanoacetic acids and its derivatives 7. This transition‐metal‐catalyzed reaction generates metal nucleophiles, which can then react with a variety of electrophilic reagents, such as aryl halides,7a,b aryl triflates,7a benzyl electrophiles,7c aldehydes,7d imines,7d,e and isatin7f,g to construct cyano compounds (Scheme a). In sharp contrast with previous results, cyanoacetic acid is envisioned as a masked electrophile herein, and used to react with nucleophiles using Bu 4 NI as a catalyst and t BuOOH as an oxidant (Scheme b) 8.…”

Synthesis of Arylacetates from Benzylic Alcohols and Oxalate Esters through Decarboxylative Coupling

“…The overall reaction (Scheme , top), in which CO 2 and ethanol are the only byproducts, compares favorably with classical arylacetic acid syntheses such as the hydrolysis of benzyl cyanides and the transition metal catalyzed carbonylation of benzylic halides or alcohols 15. It is also a valuable alternative to modern arylacetic acid syntheses, involving, for example, the oxidative carbonylation of toluene,16 the oxidation of terminal alkynes,17 the electrocatalytic carboxylation of benzyl halides,18 transition metal catalyzed cross‐coupling reactions between aryl halides and enolates,19 malonates,20 cyanoacetates,21 or acetoacetates,22 carbene‐transfer reactions from ethyl diazoacetate,23 and coupling reactions of α‐haloacetate esters,24 each of which have their individual drawbacks.…”