title: Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide.
abstract: The oxidation of arenes by the reagent phthaloyl peroxide provides a new method for the synthesis of phenols. A new, more reactive arene oxidizing reagent, 4,5-dichlorophthaloyl peroxide, computationally predicted and experimentally determined to possess enhanced reactivity, has expanded the scope of the reaction while maintaining a high level of tolerance for diverse functional groups. The reaction proceeds through a novel "reverse-rebound" mechanism with diradical intermediates. Mechanistic insight was achieved through isolation and characterization of minor byproducts, determination of linear free energy correlations, and computational analysis of substituent effects of arenes, each of which provided additional support for the reaction proceeding through the diradical pathway.
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Camelio
authors.forename: Yong
authors.initials: Y
authors.lastname: Liang
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.|§Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego, La Jolla, California 92037, United States.
authors.forename: Anders M
authors.initials: AM
authors.lastname: Eliasen
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.|§Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego, La Jolla, California 92037, United States.
authors.forename: Trevor C
authors.initials: TC
authors.lastname: Johnson
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Changxia
authors.initials: C
authors.lastname: Yuan
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Alex W
authors.initials: AW
authors.lastname: Schuppe
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.|§Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego, La Jolla, California 92037, United States.
authors.forename: Dionicio
authors.initials: D
authors.lastname: Siegel
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D006900:Hydroxylation; D015394:Molecular Structure; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry*; D010795:Phthalic Acids / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: C000603243:4,5-dichlorophthaloyl peroxide; D001555:Benzene Derivatives; D010545:Peroxides; D010795:Phthalic Acids; C000596643:phthaloyl peroxide