1,1-Carboamination of Terminal Alkenes via a Reaction of Azo-Ene Adducts with Grignard Reagents

Abstract

Facile conversion of petrochemical feedstocks into valuable amine molecules remains a long-standing challenge in organic chemistry. Here, we report a modular and practical alkene 1,1-carboamination technology that relies on sequential azo-ene reactions and attendant base-promoted N−N bond cleavage of azoene adducts with Grignard reagents. By employing allylic urazoles as imine surrogates, this method bypasses the conventional retrosynthetic logic of imine synthesis, thereby allowing for rapid access to diverse α-branched allylic amine derivatives.

Site selective gold(i)-catalysed benzylic C–H amination via an intermolecular hydride transfer to triazolinediones

“… 1 The Alder–ene reaction is formally an insertion of a urazole moiety into an allylic C–H bond, with concomitant displacement of the olefinic bond ( Scheme 1a ). 2 Direct C–H amination reactivity with triazolinediones is also known in electrophilic aromatic substitutions, 3 a – f and for ‘enolisable’ C–H bonds. 3 g Direct insertions of triazolinediones into weak C–H bonds, such as thio-ether α-hydrogens, are known to proceed via a free radical substitution chain reaction involving hydrogen atom abstraction by a nitrogen-centred radical species.…”