Photo-Promoted Decarboxylative Alkylation of α,β-Unsaturated Carboxylic Acids with ICH₂CN for the Synthesis of β,γ-Unsaturated Nitriles

Abstract

An efficient, catalyst/photocatalyst-free, and cost-effective methodology for the decarboxylative alkylation of α,β-unsaturated carboxylic acids to synthesize β,γ-unsaturated nitriles has been developed. The reaction proceeded in an environmentally benign atmosphere of blue light-emitting diode irradiation with K2CO3 and water at room temperature. The methodology worked for a wide range of substrates (22 examples) with up to 83% yield. The protocol is also compatible for gram-scale synthesis.

The stable “F–SO2+” donor provides a mild and efficient approach to nitriles and amides

“…Owing to their widespread applications, there has been a push in recent decades to develop a more efficient, mild, Rosenmund–von Braun and safe approach to nitriles and amides. Sandmeyer and Braun reactions, 7 formal acid–nitrile exchange, 8 transition-metal-catalyzed cyanation of halides, 9 and direct C–H cyanation are examples of traditional cyanide-based processes to nitriles ( Scheme 2a(1) ). 10 Meanwhile, many cyanide-free synthetic methods have been developed, such as amide dehydration, 11 primary amine hydrogenation, 12 and cyanation with other nitrogen sources.…”

Halogen-bonding-promoted Photo-induced C–X Borylation of Aryl Halide using Phenol Derivatives

“…[28] At the same time, 7b is formed by the reaction of TEMPO with the acetonitrile radical generated by the hydrogen atom abstraction from acetonitrile by the phenoxy radical generated in situ. [29] I Based on the previously reported results and our experimental evidence, the possible reaction pathway for generating the aryl radical is shown in Scheme 3. [5e, 23,25,30] The reaction was initiated by photoexcitation of the halogen-bonding complex A to produce the excited state B under irradiation of 420 nm LED.…”

Metal‐Free Visible‐Light‐Induced Atom‐Transfer Radical Addition Reaction of Alkenes/Alkynes with ICH2CN

“…[ 11 ] Our group developed a visible light‐induced decarboxylative cyanomethylation of α,β ‐unsaturated carboxylic acids with iodoacetonitrile for the synthesis of β , γ ‐unsaturated nitriles in moderate to high yields under mild reaction conditions. [ 12 ] In continuation of our work, we herein report the visible‐light‐induced metal/photo‐catalyst free ATRA reaction of alkenes and alkynes with ICH 2 CN.…”