4383-22-6Relevant articles and documents
Thermal Cyclodimerization of Aliphatic Secondary C,N-Dilithioallylamine Derivatives
Barluenga, Jose,Canteli, Rosa-Maria,Florez, Josefa
, p. 3753 - 3757 (1996)
β-Nitrogen-functionalized vinylic organolithium compounds derived from secondary aliphatic allylamines have been found to undergo upon heating (reflux of THF) either a dimerization or a regio- and stereoselective cyclodimerization reaction affording diamino 1,4-dienes or cis-2,3-disubstituted 4-methylenepyrrolidines, respectively, according to reaction time.In contrast, the corresponding dianions derived from aromatic allylamines underwent protonation by the solvent under analogous thermal treatment.A mechanism accounting for all these results has been proposed, which involves a spontaneous β-elimination of lithium hydride and an intramolecular nucleophilic cyclization by addition of a lithium amide to an alkene group as critical steps.In addition, experimental evidence is provided about the formation of 3-lithio-1-aza 1,3-dienes as intermediates in these unusual thermal transformations.
Integrated Electro-Biocatalysis for Amine Alkylation with Alcohols
Pe?afiel, Itziar,Dryfe, Robert A. W.,Turner, Nicholas J.,Greaney, Michael F.
, p. 864 - 867 (2021/01/21)
The integration of electro and bio-catalysis offers new ways of making molecules under very mild, environmentally benign conditions. We show that TEMPO mediated electro-catalytic oxidation of alcohols can be adapted to work in aqueous buffers, with minimal organic co-solvent, enabling integration with biocatalytic reductive amination using the AdRedAm enzyme. The combined process offers a new approach to amine alkylation with native alcohols, a key bond formation in the chemical economy that is currently achieved via precious metal-catalyzed hydrogen-borrowing technologies. The electrobio transformation is effective for primary and secondary alcohols undergoing coupling with allyl, propargyl, benzyl, and cyclopropyl amines, and has been adapted for use with solid-supported AdRedAm for ease of operation.
Lanthanide-Catalyzed Tandem Addition of Amines to Cyanoalkenes: Synthesis of Cyclic Amidines
Chai, Zhuo,Hou, Jinsong,Yang, Gaosheng
supporting information, (2022/01/04)
A tandem insertion of aliphatic nitriles and unactivated alkenes to the N-H bond of secondary aliphatic amines catalyzed by simple trialkyl rare-earth metal complexes was disclosed. This reaction provides a highly atom-economic and stereoselective way to a range of cyclic amidines under mild reaction conditions.
