title: Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction.
abstract: Using rational ligand design, we have developed of a second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine, for the preparation of allylsilanes using the palladium-catalyzed silyl-Heck reaction. This new ligand provides nearly complete suppression of starting material alkene isomerization that was observed with our first-generation catalyst, providing vastly improved yields of allylsilanes from simple alkene starting materials. The studies quantifying the electronic and steric properties of the new ligand are described. Finally, we report an X-ray crystal structure of a palladium complex resulting from the oxidative addition of Me3SiI using an analogous ligand that provides significant insight into the nature of the catalytic system.
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Jesse R
authors.initials: JR
authors.lastname: McAtee
authors.forename: Glenn P A
authors.initials: GP
authors.lastname: Yap
authors.forename: Donald A
authors.initials: DA
authors.lastname: Watson
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D007202:Indicators and Reagents; D007536:Isomerism; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry
chemical_list: D000475:Alkenes; D007202:Indicators and Reagents; D008024:Ligands; D012821:Silanes; D014753:Vinyl Compounds; C511847:allylsilane; D010165:Palladium