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

Publication: Research - peer-reviewJournal article – Annual report year: 2006

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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
Publication date2006
Volume12
Journal number20
Pages5352-5360
ISSN0947-6539
DOIs
StatePublished
CitationsWeb of Science® Times Cited: 32
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