Regio- and Diastereoselective Rhodium-Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles

Abstract

We have developed a highly regio- and diastereoselective rhodium-catalyzed allylic substitution of challenging alkyl-substituted secondary allylic carbonates with benzylzinc reagents, which are prepared from widely available benzyl halides. This process utilizes rhodium(III) chloride as a commercially available, high-oxidation state and bench-stable pre-catalyst to provide a rare example of a regio- and diastereoselective allylic substitution in the absence of an exogenous ligand. This reaction tolerates electronically diverse benzylzinc nucleophiles and an array of functionalized and/or challenging aliphatic allylic electrophiles. Finally, the configurational fluxionality of the rhodium-allyl intermediate is exploited to develop a novel diastereoselective process for the construction of vicinal acyclic ternary/ternary stereogenic centers, in addition to a cyclic ternary/quaternary derivative.