Change search
ReferencesLink to record
Permanent link

Direct link
On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory
Department of Chemistry, Technical University of Denmark.ORCID iD: 0000-0002-1553-4027
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, no 50, 12862-12867 p.Article in journal (Refereed) Published
Abstract [en]

The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex with two phosphine ligands, the corresponding neutral complex with one phosphine and one chloride ligand, and a neutral eta(1)-allylPd complex with one chloride and two phosphine ligands. The eta(1)-complex is unreactive toward nucleophiles. The cationic eta(3)-complex is the intermediate most frequently invoked in the title reaction, but in the presence of halides, the neutral, unsymmetrically substituted eta(3)-CoMplex will be formed rapidly from anionic Pd(0) complexes in solution. Since the latter will prefer both leaving group ionization and reaction with nucleophiles in the position trans to phosphorus, it can rationalize the observed "memory effect" (a regioretention) in the title reaction, even in the absence of chiral ligands.

Place, publisher, year, edition, pages
2008. Vol. 112, no 50, 12862-12867 p.
National Category
Organic Chemistry
URN: urn:nbn:se:kth:diva-48875DOI: 10.1021/jp801759zISI: 000261652800019OAI: diva2:488422
QC 20120215Available from: 2012-02-01 Created: 2011-11-23 Last updated: 2012-02-15Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Ahlquist, Mårten
In the same journal
Journal of Physical Chemistry A
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 20 hits
ReferencesLink to record
Permanent link

Direct link