Sterically Demanding Oxidative Amidation of α‐Substituted Malononitriles with Amines Using O2
نویسندگان
چکیده
An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical formation of α-peroxy malononitrile species, which can cyclize to dioxiranes that can monooxygenate malononitrile α-carbanions to afford activated acyl cyanides capable of reacting with amine nucleophiles.
منابع مشابه
Iron-catalysed oxidative amidation of alcohols with amines.
A new iron-catalysed oxidative amidation of differently substituted benzylic alcohols with mono- and di-substituted amines was developed.
متن کاملKinetic resolution of primary allylic amines via palladium-catalyzed asymmetric allylic alkylation of malononitriles.
A range of primary allylic amines were resolved with selectivity factors of up to 491 through [Pd(allyl)Cl]2/(S)-BINAP-catalyzed and mesitylsulfonyl hydrazide-accelerated asymmetric allylic alkylation of malononitriles involving enantioselective C-N bond cleavage under aerobic conditions. Moreover, the reaction proved useful for the asymmetric synthesis of α-branched allyl-substituted malononit...
متن کاملPreparation of sterically congested 1,3,4-oxadiazole derivatives from N-isocyaniminotriphenylphosphorane, aromatic acids, cyclopentanone and primary amines
Reactions of N-isocyaniminotriphenylphosphorane with cyclopentanone have been studied in the presence of aromatic carboxylic acids and primary amines, proceeds smoothly at room temperature under neutral conditions to afford sterically congested 1,3,4-oxadiazole derivatives by an intramolecular Aza-Wittig cyclization in CH2Cl2 in excellent yields. The structures of the products were deduced from...
متن کاملTungstophosphoric Acid Supported on Silica-encapsulated γ-Fe2O3 Nanoparticles Catalyzed Oxidative Amidation
We have used tungestophosphoric acid to catalyze oxidative amidation reaction from benzyl alcohols and methylarens with hydrochloride salts of amines. To achieve this purpose, modified magnetic nanoparticles (γ-Fe2O3@SiO2@H3PW12O40) were applied as catalyst and TBHP as external oxidant. After optimizing, different derivates of be...
متن کاملYttrium-catalysed dehydrocoupling of alanes with amines.
We report [Y{N(SiMe3)2}3] as a precatalyst for the dehydrocoupling of sterically demanding amines with β-diketiminate stabilised aluminium dihydrides. While simple fluorinated anilines readily undergo Al-H/N-H dehydrocoupling under thermal conditions, catalytic methods are required to achieve reasonable rates of reaction for ortho-substituted anilines or hindered aliphatic amines.
متن کامل