Electronic Control of the Regiochemistry in the Heck Reaction
- 1 March 2003
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (12) , 3503-3508
- https://doi.org/10.1021/ja028755o
Abstract
The migratory insertion of propene into the Pd-phenyl bond of a set of neutral palladium(II) complexes with N-N, P-O, and N-O chelating ligands has been investigated by using density functional methods. In contrast to cationic palladium(II)-diimine complexes, which favor 1,2-insertion, the more electron-rich neutral complexes lead to 2,1-insertion. Trans influences are substantial in the unsymmetrical ligand systems, primarily affecting the insertion barrier. Introducing steric effects leads toward improving 1,2-selectivity, due to destabilization of the 2,1-transition state. Electronic and steric influences can be systematically combined to control the regiochemistry in the Heck reaction.Keywords
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