1213-69-0Relevant articles and documents
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.
Metalation of iminium ions formed in the reaction of tertiary amines with TiCl4
Bharathi, Pandi,Periasamy, Mariappan
, p. 857 - 859 (2008/02/09)
(equation presented) TiCl4 reacts with trialkylamines at 0-25°C to give iminium ions that on metalation followed by reaction with diaryl ketones, produce α,β-unsaturated aldehydes.
IMINE ANIONS DERIVED FROM 20 ALLYLIC AMINES
Carlson, R. M.,Hewetson, D. W.,Deeg, M. A.,Mix, G. R.,Liu, T. L.
, p. 1017 - 1024 (2007/10/02)
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