Deconvoluting the memory effect in Pd-catalyzed allylic alkylation; effect of leaving group and added chloride

Peter Fristrup, Thomas Jensen, Jakob Hoppe, Per-Ola Norrby

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An analysis of product distributions in the Tsuji-Trost reaction indicates that several instances of reported memory effects can be attributed to slow interconversion of the initially formed syn- and anti-[Pd(eta3-allyl)] complexes. Addition of chloride triggers a true memory effect, in which the allylic terminus originally bearing the leaving group has a higher reactivity. The latter effect, termed regioretention, can be rationalized by ionization from a palladium complex bearing a chloride ion, forming an unsymmetrically substituted [Pd(eta3-allyl)] complex. DFT calculations verify that the position trans to the phosphine ligand is more reactive both in the initial ionization and in the subsequent nucleophilic attack.
Original languageEnglish
JournalChemistry: A European Journal
Issue number20
Pages (from-to)5352-5360
Publication statusPublished - 2006

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