title: Pd(II)-catalyzed C-H functionalizations directed by distal weakly coordinating functional groups.
abstract: Ortho-C(sp(2))-H olefination and acetoxylation of broadly useful synthetic building blocks phenylacetyl Weinreb amides, esters, and ketones are developed without installing an additional directing group. The interplay between the distal weak coordination and the ligand-acceleration is crucial for these reactions to proceed under mild conditions. The tolerance of longer distance between the target C-H bonds and the directing functional groups also allows for the functionalizations of more distal C-H bonds in hydrocinnamoyl ketones, Weinreb amides, and biphenyl Weinreb amides. Mechanistically, the coordination of these carbonyl groups and the bisdentate amino acid ligand with Pd(II) centers provides further evidence for our early hypothesis that the carbonyl groups of the potassium carboxylate are responsible for the directed C-H activation of carboxylic acids.
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Gang
authors.initials: G
authors.lastname: Li
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Li
authors.initials: L
authors.lastname: Wan
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Guofu
authors.initials: G
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Dasheng
authors.initials: D
authors.lastname: Leow
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Jillian
authors.initials: J
authors.lastname: Spangler
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Jin-Quan
authors.initials: JQ
authors.lastname: Yu
mesh_terms: D000475:Alkenes / Q000737:chemistry; D000577:Amides / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010666:Phenylpropionates / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000577:Amides; D007659:Ketones; D010666:Phenylpropionates; D010165:Palladium; D002244:Carbon; D006859:Hydrogen