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Updated: Dec 11, 2025

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Regio- and Diastereoselective Rhodium-Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles
Debasis Pal1, Timothy B Wright1, Ryan O'Connor2
1Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ON, K7L 3N6, Canada.
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.
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