38167-88-3Relevant articles and documents
Synthesis of a bicyclic oxo-γ-lactam from a simple caprolactam derivative
Weck, Christian,Obst, Franziska,Nauha, Elisa,Schofield, Christopher J.,Gruber, Tobias
, p. 9984 - 9989 (2017)
The synthesis of the 6-azabicyclo[3.2.1]octane ring system, via Dieckmann cyclization, is described. Ring closure involves reaction of a caprolactam enolate with a C-6 ester, the reactive axial conformation of which is promoted by the presence of an N-tert-butyloxycarbonyl group on the lactam nitrogen. The results will enable the synthesis of new bridged caprolactams for testing as antibacterials and nucleophilic enzyme inhibitors.
Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. a Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion
Benati, Luisa,Nanni, Daniele,Sangiorgi, Corrado,Spagnolo, Piero
, p. 7836 - 7841 (2007/10/03)
A variety of acyclic and carbocyclic α-azido-β-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific β-scission to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxycarbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.
