Anti‐Markovnikov Hydroamination and Hydroalkoxylation of Allylic Alcohols Promoted by a Simple Rare‐Earth Metal Trialkyl Complex

Abstract An exclusive anti ‐Markovnikov hydroamination as well as hydroalkoxylation of allylic alcohols catalyzed by a simple catalyst Y(CH 2 SiMe 3 ) 3 (THF) 2 has been developed, providing a variety of γ‐amino and γ‐alkoxy alcohols in good yields under mild conditions. Moreover, this protocol is applied to the synthesis of drug molecules Propipocaine and Proroxan . The rare‐earth metal catalyst features readily available, wide substrate compatability, exclusive anti ‐Markovnikov selectivity, and performs in the absence of a base or an additive.