Journal article
Deconvoluting the memory effect in Pd-catalyzed allylic alkylation; effect of leaving group and added chloride
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.
Language: | English |
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Publisher: | WILEY-VCH Verlag |
Year: | 2006 |
Pages: | 5352-5360 |
ISSN: | 15213765 and 09476539 |
Types: | Journal article |
DOI: | 10.1002/chem.200600152 |
ORCIDs: | Fristrup, Peter |