Tandem catalytic allylic C-H amination and asymmetric [2,3]-rearrangement via bimetallic relay catalysis

A bimetallic relay catalysis protocol for tandem allylic C-H amination and asymmetric [2,3]-sigmatropic rearrangement has been developed with the use of an achiral Pd⁰ catalyst and a chiral N,N'-dioxide-Mg^II complex in a one-pot operation. A series of anti-α-amino derivatives containing two stereogenic centers were prepared from readily available allylbenzenes and glycine pyrazolamide with good yields and high stereoselectivities. Moreover, the synthetic potential of this protocol was further demonstrated by the product transformations, and a catalytic cycle was proposed to illustrate the reaction process.