82946-80-3Relevant articles and documents
Electrochemical Aziridination of Internal Alkenes with Primary Amines
Bartolomeu, Aloisio de A.,Dyga, Marco,Goo?en, Lukas J.,Laudadio, Gabriele,No?l, Timothy,O?eka, Maksim,de Bruin, Bas,de Oliveira, Kleber T.,van Leest, Nicolaas P.
supporting information, p. 255 - 266 (2021/01/19)
An electrochemical approach to prepare aziridines via an oxidative coupling between alkenes and primary alkyl amines was realized. The reaction is carried out in an electrochemical flow reactor, leading to short reaction/residence times (5 min), high yields, and broad scope. At the cathode, hydrogen is generated, which can be used in a second reactor to reduce the aziridine yielding the corresponding hydroaminated product.Aziridines are useful synthetic building blocks, widely employed for the preparation of various nitrogen-containing derivatives. As the current methods require the use of prefunctionalized amines, the development of a synthetic strategy toward aziridines that can establish the union of alkenes and amines would be of great synthetic value. Herein, we report an electrochemical approach, which realizes this concept via an oxidative coupling between alkenes and primary alkylamines. The reaction is carried out in an electrochemical flow reactor leading to short reaction/residence times (5 min), high yields, and broad scope. At the cathode, hydrogen is generated, which can be used in a second reactor to reduce the aziridine, yielding the corresponding hydroaminated product. Mechanistic investigations and DFT calculations revealed that the alkene is first anodically oxidized and subsequently reacted with the amine coupling partner.The central tenet in modern synthetic methodology is to develop new methods only using widely available organic building blocks. As a direct consequence, new activation strategies are required to cajole the coupling partners to react and, subsequently, forge new and useful chemical bonds. Using electrochemical activation, our methodology enables for the first time the direct coupling between olefins and amines to yield aziridines. Aziridines display interesting pharmacological activity and serve as valuable synthetic intermediates to prepare diverse nitrogen-containing derivatives. Interestingly, the sole byproduct generated in this process is hydrogen, which can be subsequently used to reduce the aziridine into the corresponding hydroaminated product. Hence, this electrochemical methodology can be regarded as green and sustainable from the vantage point of upgrading simple and widely available commodity chemicals.
DMF Dimethyl Acetal as Carbon Source for α-Methylation of Ketones: A Hydrogenation-Hydrogenolysis Strategy of Enaminones
Borah, Ashwini,Goswami, Limi,Neog, Kashmiri,Gogoi, Pranjal
, p. 4722 - 4728 (2015/05/13)
A novel heterogeneous catalytic hydrogenation-hydrogenolysis strategy has been developed for the α-methylation of ketones via enaminones using DMF dimethyl acetal as carbon source. This strategy provides a very convenient route to α-methylated ketones using a variety of ketones without any base or oxidant. (Chemical Equation Presented).
Bidentate Schiff bases derived from (S)-α-methylbenzylamine as chiral ligands in the electronically controlled asymmetric addition of diethylzinc to aldehydes
Jaworska, Magdalena,Welniak, Miroslaw,Zieciak, Justyna,Kozakiewicz, Anna,Wojtczakb, Andrzej
experimental part, p. 189 - 204 (2011/08/21)
A group of bidentate Schiff bases derived from enantiomerically pure (S)-α-methylbenzylamine was synthesized. Crystal structure was determined for three compounds. Schiff bases were used as chiral ligands in the asymmetric addition of Et2Zn to aldehydes. The obtained enantioselectivity was e.e.=8-94% depending on the substrate and the best was observed for (S,E)-2-(1-(1-phenylethylimino)-ethyl)phenol. The enantioselectivity increase was connected with the substituent-induced electronic effects in the substrate molecules. Molecular modeling resulted in the models of the 3D structures of Zn-Zn complex catalysts containing investigated Schiff bases, which were consistent with the reported chirality of the addition product and explained observed e.e. The presented transition state models allow explaining the change of the absolute configuration of diethylzinc addition product in the case of using ortho-substituted aldehydes. ARKAT-USA, Inc.
