title: Palladium-catalyzed asymmetric allylic alkylations of polynitrogen-containing aromatic heterocycles.
abstract: We report the palladium-catalyzed asymmetric allylic alkylation (AAA) reaction of a variety of nitrogen-containing aromatic heterocycles, including pyrazine, pyrimidine, pyridazine, quinoxaline, and benzoimidazole derivatives. The mesityl ester, whose steric bulk prevents competitive deacylation of the electrophile from "hard" nucleophiles, is introduced as a new leaving group in allylic alkylation chemistry. In contrast to our previous studies of AAA reactions with pyridine-based substrates, no precomplexation with a Lewis acid is required before deprotonation with LiHMDS, underscoring the relative acidity of these electron-deficient nucleophiles.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305-5080, United States. bmtrost@stanford.edu
authors.forename: Barry M
authors.initials: BM
authors.lastname: Trost
authors.forename: David A
authors.initials: DA
authors.lastname: Thaisrivongs
authors.forename: Jan
authors.initials: J
authors.lastname: Hartwig
mesh_terms: D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D006574:Heterocyclic Compounds, 2-Ring / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*
chemical_list: D000498:Allyl Compounds; D006573:Heterocyclic Compounds, 1-Ring; D006574:Heterocyclic Compounds, 2-Ring; D010165:Palladium; D009584:Nitrogen