42142-19-8Relevant academic research and scientific papers
Tertiary amine synthesis: Via reductive coupling of amides with Grignard reagents
Xie, Lan-Gui,Dixon, Darren J.
, p. 7492 - 7497 (2017/10/30)
A new iridium catalyzed reductive coupling reaction of Grignard reagents and tertiary amides affording functionalised tertiary amine products via an efficient and technically-simple one-pot, two-stage experimental protocol, is reported. The reaction-which can be carried out on gram-scale using as little as 1 mol% Vaska's complex [IrCl(CO)(PPh3)2] and TMDS as the terminal reductant for the initial reductive activation step-tolerates a broad range of tertiary amides from (hetero)aromatic to aliphatic (branched, unbranched and formyl) and a wide variety of alkyl (linear, branched), vinyl, alkynyl and (hetero)aryl Grignard reagents. The new methodology has been applied directly to bioactive molecule synthesis and the high chemoselectivity of the reductive coupling of amide has been exploited in late stage functionalization of drug molecules. This reductive functionalisation of tertiary amides provides a new and practical solution to tertiary amine synthesis.
Chemical Behavior of N-Alkyl-N-methylbenzylammonium N-Alkylide
Okazaki, Seiji,Shirai, Naohiro,Sato, Yoshiro
, p. 334 - 337 (2007/10/02)
N-Alkyl-N-methyl(4-substituted benzyl)ammonium N-alkylides (3), produced by fluoride ion induced desilylation of N-alkyl-N-methyl-N-(4-substituted benzyl)-1-(trimethylsilyl)alkylammonium iodides (2), were mainly converted into N-alkyl-N-methyl-1-(4-substituted benzyl)alkylamines (5, Stevens rearrangement products) and 4-substituted toluenes (8).Both compounds were produced via radical-forming and -destroying pathways from 2-substituted-6--5-methylene-1,3-cylohexadienes (4), which were initially formed from 3 by sigmatropic rearrangement.There is no direct migration pathway from 3 to 5.
