211378-87-9Relevant academic research and scientific papers
Achieving control over the branched/linear selectivity in palladium-catalyzed allylic amination
Dubovyk, Igor,Watson, Iain D. G.,Yudin, Andrei K.
, p. 1559 - 1575 (2013/03/28)
Palladium-catalyzed reaction of unsymmetrical allylic electrophiles with amines gives rise to regioisomeric allylic amines. We have found that linear products result from the thermodynamically controlled isomerization of the initially formed branched products. The isomerization is promoted by protic acid and active palladium catalyst. The use of base shuts down the isomerization pathway and allows for the preparation and isolation of branched allylic amines. Solvent plays a key role in achieving high kinetic regioselectivity and in controlling the rate of isomerization. The isomerization can be combined with ring-closing metathesis to afford the synthesis of exocyclic allylic amines from their endocyclic precursors.
Palladium-catalyzed ring-contraction and ring-expansion reactions of cyclic allyl amines
Dubovyk, Igor,Pichugin, Dmitry,Yudin, Andrei K.
supporting information; experimental part, p. 5924 - 5926 (2011/08/04)
Ring around the rosy: An amino group can act as the leaving group or the nucleophile in a palladium-catalyzed allylic amination. As a result, readily accessible cyclic amines can be either ring contracted or ring expanded (see scheme).
Chasing the proton culprit from palladium-catalyzed allylic amination
Dubovyk, Igor,Watson, Iain D. G.,Yudin, Andrei K.
, p. 14172 - 14173 (2008/09/18)
We have found that the addition of base has a significant effect on palladium-catalyzed allylic amination. The long-standing problem of controlling the branched-to-linear ratio has been solved. In the presence of DBU and inexpensive, readily available ligands, palladium-catalyzed allylation proceeds under kinetic control, leading to high branched selectivity. Given the widespread utility of palladium-catalyzed allylic amination, we expect that these findings will be relevant in many areas ranging from asymmetric catalysis to target-oriented synthesis. Copyright
