24068-20-0Relevant academic research and scientific papers
Direct Reductive N-Functionalization of Aliphatic Nitro Compounds
Rauser, Marian,Ascheberg, Christoph,Niggemann, Meike
, p. 3970 - 3974 (2018/02/26)
The first general protocol for the direct reductive N-functionalization of aliphatic nitro compounds is presented. The nitro group is partially reduced to a nitrenoid, with a mild and readily available combination of B2pin2 and zinc organyls. Thereby, the formation of an unstable nitroso intermediate is avoided, which has so far severely limited reductive transformations of aliphatic nitro compounds. The reaction is concluded by an electrophilic amination of zinc organyls.
Facile Synthesis and Isolation of Secondary Amines via a Sequential Titanium(IV)-Catalyzed Hydroamination and Palladium-Catalyzed Hydrogenation
Lui, Erica K. J.,Schafer, Laurel L.
supporting information, p. 713 - 718 (2016/03/09)
An atom economical and catalytic route for the synthesis of aryl- and alkyl-substituted secondary amines has been developed. Using a bis(amidate)bis(amido)titanium(IV) precatalyst, the hydroamination of terminal alkynes with a range of amines results in the selective formation of the anti-Markovnikov product. The crude enamine/imine mixtures are effectively hydrogenated using palladium on carbon (Pd/C) and H2 to afford the corresponding secondary amine in excellent yields. Simple work-up procedures allow for the isolation of pure compounds while avoiding purification via column chromatography.
Cesium effect: High chemoselectivity in direct N-alkylation of amines
Salvatore, Ralph Nicholas,Nagle, Advait S.,Kyung, Woon Jung
, p. 674 - 683 (2007/10/03)
A novel method for the mono-N-alkylation of primary amines, diamines, and polyamines was developed using cesium bases in order to prepare secondary amines efficiently. A cesium base not only promoted alkylation of primary amines but also suppressed overalkylations of the produced secondary amines. Various amines, alkyl bromides, and alkyl sulfonates were examined, and the results demonstrated this methodology was highly chemoselective to favor mono-N-alkylation over dialkylation. In particular, use of either sterically demanding substrates or amino acid derivatives afforded the secondary amines exclusively, offering wide applications in peptidomimetic syntheses.
Cesium Hydroxide Promoted Chemoselective N-Alkylation for the Generally Efficient Synthesis of Secondary Amines
Salvatore, Ralph N.,Nagle, Advait S.,Schmidt, Shaun E.,Jung, Kyung Woon
, p. 1893 - 1896 (2008/02/11)
(Matrix presented) Selective N-alkylation of primary amines was developed using cesium hydroxide to prepare various secondary amines efficiently. A cesium base not only promoted monoalkylations of primary amines but also suppressed overalkylations. Various amines and alkyl bromides were examined, and the preliminary results demonstrated this methodology was highly chemoselective, favoring mono-N-alkylation over dialkylation. In particular, use of amino acid derivatives afforded the desired secondary amines exclusively.
