69097-27-4Relevant academic research and scientific papers
Iridium-Catalyzed Reductive Strecker Reaction for Late-Stage Amide and Lactam Cyanation
Fuentes de Arriba, ángel L.,Lenci, Elena,Sonawane, Mahendra,Formery, Odilon,Dixon, Darren J.
supporting information, p. 3655 - 3659 (2017/03/21)
A new iridium-catalyzed reductive Strecker reaction for the direct and efficient formation of α-amino nitrile products from a broad range of (hetero)aromatic and aliphatic tertiary amides, and N-alkyl lactams is reported. The protocol exploits the mild and highly chemoselective reduction of the amide and lactam functionalities using IrCl(CO)[P(C6H5)3]2 (Vaska's complex) in the presence of tetramethyldisiloxane, as a reductant, to directly generate hemiaminal species able to undergo substitution by cyanide upon treatment with TMSCN (TMS=trimethylsilyl). The protocol is simple to perform, broad in scope, efficient (up to 99 % yield), and has been successfully applied to the late-stage functionalization of amide- and lactam-containing drugs, and naturally occurring alkaloids, as well as for the selective cyanation of the carbonyl carbon atom linked to the N atom of proline residues within di- and tripeptides.
Oxidative nucleophilic substitution of hydrogen in nitroarenes with phenylacetonitrile derivatives
Makosza, Mieczyslaw,Stalinski, Krzysztof
, p. 8797 - 8810 (2007/10/03)
Tertiary carbanions generated from α-substituted phenylacetonitriles in liquid ammonia add to nitrobenzenes in the para position to form the corresponding σ(H)-adducts which are transformed, depending on the starting nitriles and the reaction conditions, to products of oxidative nucleophilic substitution of hydrogen, ONSH or vicarious nucleophilic substitution, VNS.
