Deconvoluting the Memory Effect in Pd‐Catalyzed Allylic Alkylation: Effect of Leaving Group and Added Chloride
- 28 June 2006
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 12 (20) , 5352-5360
- https://doi.org/10.1002/chem.200600152
Abstract
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(η3-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(η3-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.Keywords
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