The palladium catalyzed di-functionalization of alkenes containing hydroxy and amino groups has been established as an effective synthetic approach to access a diverse range of heterocycles and other highly functionalized compounds [1,2]. Recently, our group has demonstrated the expedient use of trifluoroacetaldehyde-tethered hydroxy and amino nucleophiles in the Pd0 catalyzed difunctionalization of alkenes using either an alkynyl bromide or aryl iodide as electrophile. This approach, when applied to allylic amines and alcohols, gave acess to a range of vicinal amino alcohols [3,4] or diamines [5]. The resultant aminals and acetals could be hydrolysed to give rise to the free aminoalcohols. Herein, the extension of this strategy to propargylic amines to synthesise highly substituted enynes and complex α-amino ketone derivatives is presented. The generated oxazolines could be further transformed into a range of different compounds[6]. During the development of this method, a carboxylation alkynylation reaction using carbonate salt as carbon source was discovered serendipitously and gave access to oxazolidinones[7].

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[3] U. Orcel, J. Waser, Angew. Chem., Int. Ed. 2015, 54, 5250-5254.
[4] B. Muriel, U. Orcel, J. Waser, Org. Lett. 2017, 19, 3548–3551.
[5] U. Orcel, J. Waser, Angew. Chem., Int. Ed. 2016, 55, 12881-12885.
[6] P. D. G. Greenwood, E. Grenet, J, Waser, Chem. Eur. J. 2019, 25, 3010 –3013.
[7] P. D. G. Greenwood, J, Waser, Eur. J. Org. Chem. 2019 10.1002/ejoc.201900500