6319-84-2Relevant articles and documents
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.
Metallation of benzylic amines via amine-borane complexes
Ebden, Mark R.,Simpkins, Nigel S.,Fox, David N.A.
, p. 12923 - 12952 (2007/10/03)
Formation of borane complexes of N,N-dimethylbenzylamine, N,N- dimethyl(1-naphthyl)methylamine, N,N-dimethyl(2-naphthyl)methylamine, N- methyltetrahydroisoquinoline and N-methylisoindoline facilitates regioselective metallation of these systems using BuLi, giving intermediate benzylic anions which react with a range of electrophiles to give products in good yield.
Activation of Benzylic Amines Towards Regioselective Metallation by Borane Complex Formation
Ebden, Mark R.,Simpkins, Nigel S.,Fox, David N. A.
, p. 8697 - 8700 (2007/10/02)
Formation of borane complexes of N,N-dimethylbenzylamine 4 and N-methyltetrahydroisoquinoline 1 facilitates regioselective metallation of these systems using BuLi, giving benzylic anions which react with a range of electrophiles.