Isotope effects and the nature of stereo- and regioselectivity in hydroaminations of vinylarenes catalyzed by palladium(ii)-diphosphine complexes.
[reaction: see text] The hydroamination of styrene with aniline catalyzed by phosphine-ligated palladium triflates exhibits a substantial (13)C isotope effect at the benzylic carbon. This supports rate-determining nucleophilic attack of amine on a eta(3)-phenethyl palladium complex. Deuterium exchange observations and predicted isotope effects based on DFT calculations support this mechanism. Selectivity in these reactions is determined by the facility of palladium displacement after reversible hydropalladation of the alkene.
Vo
Loan K
LK
Department of Chemistry, Texas A and M University, P.O. Box 30012, College Station, Texas 77842, USA.
Singleton
Daniel A
DA
D000588:Amines / Q000737:chemistry*; D002247:Carbon Isotopes; D002384:Catalysis; D007202:Indicators and Reagents; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry
D000588:Amines; D002247:Carbon Isotopes; D007202:Indicators and Reagents; D010720:Phosphines; D014753:Vinyl Compounds; D010165:Palladium