title: Total synthesis of hibispeptin A via Pd-catalyzed C(sp3)-H arylation with sterically hindered aryl iodides.
abstract: To access the key Ile-Hpa pseudodipeptide motif in hibispeptins, a series of bidentate carboxamide-based auxiliary groups have been explored to facilitate the palladium-catalyzed arylation of unactivated γ-C(sp(3))-H bonds of Ile precursor with aryl iodides. A new pyridylmethylamine-based auxiliary group PR is introduced, which permits the use of more sterically hindered ortho-substituted aryl iodide substrates and can be removed under mild conditions. Pd-catalyzed PR-directed γ-C(sp(3))-H arylation enabled the first total synthesis of hibispeptin A.
authors.affiliation: Department of Chemistry, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Gang
authors.initials: G
authors.lastname: He
authors.forename: Shu-Yu
authors.initials: SY
authors.lastname: Zhang
authors.forename: William A
authors.initials: WA
authors.lastname: Nack
authors.forename: Ryan
authors.initials: R
authors.lastname: Pearson
authors.forename: Javon
authors.initials: J
authors.lastname: Rabb-Lynch
authors.forename: Gong
authors.initials: G
authors.lastname: Chen
mesh_terms: D002384:Catalysis; D031584:Hibiscus / Q000737:chemistry*; D006860:Hydrogen Bonding; D007454:Iodides / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry; D010456:Peptides, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D018517:Plant Roots / Q000737:chemistry*
chemical_list: D007454:Iodides; D010456:Peptides, Cyclic; C000600292:hibispeptin A; D010165:Palladium