Ring Opening of Isoprene Monoxide with Nitrogen Nucleophiles

Significance

The dynamic kinetic asymmetric transformation (DYKAT) for the ring opening of isoprene monoxide is shown to proceed with primary amine nucleophiles. The best and most useful example employed PMBNH₂ as the nucleophile and a palladium-1 complex as the catalyst. Importantly, this reaction could be scaled up to 20 mmol with only small loss of enantioselectivty (89.5% ee). The authors also used this protocol to synthesize a l-vancosamine derivative in only 11 steps.