80306-48-5Relevant academic research and scientific papers
Reduction of a 1-aza-1,3-diene to a 1-azabut-2-ene-1,4-diyl dianion: An unusual reaction course
Lorenz, Volker,Goerls, Helmar,Scholz, Joachim
, p. 2253 - 2257 (2003)
A suprising intermediate during the reduction of the 1-aza-1,3-diene 1 with lithium is the dilithium hexa-1,5-dien-1,6-diamide 2, which probably forms by dimerization of the initially generated radical anion of 1. However, the new C-C bond of 2 is not very resistant to the alkali metal and is reductively cleaved, which leads to the formation of the dark red (1-azabut-2-en-1,4-diyl)dilithium compound 3.
Palladium-Catalyzed γ,γ′-Diarylation of Free Alkenyl Amines
Fu, Yu,Grant, Aaron J.,Landge, Vinod G.,Payton, John L.,Rabon, Allison M.,Young, Michael C.
supporting information, p. 10352 - 10360 (2021/07/26)
The direct difunctionalization of alkenes is an effective way to construct multiple C-C bonds in one-pot using a single functional group. The regioselective dicarbofunctionalization of alkenes is therefore an important area of research to rapidly obtain complex organic molecules. Herein, we report a palladium-catalyzed γ,γ′-diarylation of free alkenyl amines through interrupted chain walking for the synthesis of Z-selective alkenyl amines. Notably, while 1,3-dicarbofunctionalization of allyl groups is well precedented, the present disclosure allows 1,3-dicarbofunctionalization of highly substituted allylamines to give highly Z-selective trisubsubstituted olefin products. This cascade reaction operates via an unprotected amine-directed Mizoroki-Heck (MH) pathway featuring a β-hydride elimination to selectively chain walk to furnish a new terminal olefin which then generates the cis-selective alkenyl amines around the sterically crowded allyl moiety. This operationally simple protocol is applicable to a variety of cyclic, branched, and linear secondary and tertiary alkenylamines, and has a broad substrate scope with regard to the arene coupling partner as well. Mechanistic studies have been performed to help elucidate the mechanism, including the presence of a likely unproductive side C-H activation pathway.
Modular access to vicinally functionalized allylic (thio)morpholinonates and piperidinonates by substrate-controlled annulation of 1,3-azadienes with hexacyclic anhydrides
Braunstein, Hannah,Langevin, Spencer,Khim, Monique,Adamson, Jonathan,Hovenkotter, Katie,Kotlarz, Lindsey,Mansker, Brandon,Beng, Timothy K.
supporting information, p. 8864 - 8872 (2016/10/03)
A modular substrate-controlled hexannulation of inherently promiscuous 1,3-azadienes with hexacyclic anhydrides, which affords versatile vicinally functionalized allylic lactams, in high yields, regio- and stereoselectivities is described.
