Rhodium-Catalyzed Regio- and Enantioselective Allylic Amination of Racemic 1,2-Disubstituted Allylic Phosphates
Wenbin Xu, Minghe Sun, Mouhai Shu, Changkun Li
Abstract
Alkynylphosphines are rarely used as ligands in asymmetric metal catalysis. We synthesized a series of chiral bis(oxazoline)alkynylphosphine ligands and used them in Rh-catalyzed highly regio- and enantioselective allylic amination reactions of 1,2-disubstituted allylic phosphates. Chiral 1,2-disubstituted allylic amines were synthesized in up to 95% yield with >20:1 branched/linear (b/l) ratio and 99% ee from racemic 1,2-disubstituted allylic precursors. The sterically smaller linear alkynyl group on the P atom in the bis(oxazoline)alkynylphosphine ligands was the key to fit the new requirements of the introduction of bulky 2-R′ groups.
Topics & Concepts
ChemistryAllylic rearrangementEnantioselective synthesisAminationRhodiumCatalysisOrganic chemistryRegioselectivityStereochemistryAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and CatalysisChemical Synthesis and Analysis