130457-35-1

Upstream product

• 151-50-8 potassium cyanide 
• 13734-41-3 N-Boc-(S/R)-valine 
• 172876-96-9 3-oxo-1λ³-benzo[d][1,2]iodaoxole-1(3H)-carbonitrile 
• 19158-51-1 P-toluenesulfonyl cyanide 
• 365441-87-8 3-[[(1,1-dimethylethoxy)carbonyl]amino]-2-methylpropanoic acid 
• 4248-19-5 tert-butyl carbazate 
• 130457-26-0 t-butyl  

Relevant academic research and scientific papers

Room temperature decarboxylative cyanation of carboxylic acids using photoredox catalysis and cyanobenziodoxolones: a divergent mechanism compared to alkynylation

The one-step conversion of aliphatic carboxylic acids to the corresponding nitriles has been accomplished via the merger of visible light mediated photoredox and cyanobenziodoxolones (CBX) reagents. The reaction proceeded in high yields with natural and non-natural α-amino and α-oxy acids, affording a broad scope of nitriles with excellent tolerance of the substituents in the α position. The direct cyanation of dipeptides and drug precursors was also achieved. The mechanism of the decarboxylative cyanation was investigated both computationally and experimentally and compared with the previously developed alkynylation reaction. Alkynylation was found to favor direct radical addition, whereas further oxidation by CBX to a carbocation and cyanide addition appeared more favorable for cyanation. A concerted mechanism is proposed for the reaction of radicals with EBX reagents, in contrast to the usually assumed addition elimination process.

Decarboxylative alkynylation and cyanation of carboxylic acids using photoredox catalysis and hypervalent iodine reagents

Alkynes and nitriles are important functional groups that serve as versatile building blocks in organic synthesis and find applications in material and medicinal sciences. A convenient and straightforward access to both classes of compounds under mild conditions is, therefore, highly desirable. Herein, we disclose the decarb-oxylative alkynylation and cyanation of broadly available carboxylic acids using photoredox catalysis and hyper-valent iodine reagents. Choices of both catalysts and reagents were crucial. Computational and experimental studies revealed two different possible mechanisms that are dictated by the oxidation potential of the reagents: radical for alkynylation, ionic for cyanation.

Photoinduced direct cyanation of C(sp3)-H bonds

A general and practical synthetic protocol for the direct transformation of unreactive C(sp3)-H bonds to C(sp3)-CN bonds has been developed. The homolytic cleavage of the C-H bond is initiated by photo-excited benzophenone, and the resulting carbon radical subsequently reacts with tosyl cyanide to afford the corresponding nitrile in a highly efficient manner. The present methodology is widely applicable to various starting materials including ethers, alcohols, amine derivatives, alkanes, and alkylbenzenes. This newly developed C-H cyanation protocol provides a powerful tool for selective one-carbon elongation for the construction of architecturally complex molecules. Georg Thieme Verlag Stuttgart - New York.

Photochemically induced radical transformation of C(sp3)-H bonds to C(sp3)-CN bonds

A general protocol for direct transformation of unreactive C(sp 3)-H bonds to C(sp3)-CN bonds has been developed. The C-H activation was effected by photoexcited benzophenone, and the generated carbon radical was subsequently trapped with tosyl cyanide to afford the corresponding nitrile in a highly efficient manner. The present methodology is widely applicable to versatile starting materials and, thus, serves as a powerful tool for selective one-carbon elongation for construction of architecturally complex molecules.

A convenient synthesis of N-boc-protected α-aminonitriles from α-amidosulfones

Synthesis of N-Boc-protected α-aminonitriles starting from N-Boc-protected α-aminosulfones is described. Treatment of the sulfone with two equivalents of potassium cyanide in 2-propanol or dichloromethane- H2O under phase transfer condition affords crystalline N-Boc-protected α-aminonitriles in good yield. Hydrolysis of the aminonitriles provides a convenient access to racemic α-amino acids.

Benzotriazole-assisted Synthesis of α-Acylaminonitriles and a Conceptually Novel Method for Peptide Elongation

A general method for the synthesis of α-acylamino nitriles is reported.Initially, the adducts resulting from Mannich-type condensation of benzotriazole with an aldehyde and an amide are prepared.These undergo elimination of benzotriazole with cyanide to g