Dearomatization Reactions Using Phthaloyl Peroxide.
A new oxidative dearomatization reaction has been developed using phthaloyl peroxide to chemoselectively install two oxygen-carbon bonds into aromatic precursors. The oxidation reaction proceeds only once; addition of superstoichiometric equivalents of phthaloyl peroxide does not react further with the newly generated 1,3-cyclohexadiene. The reaction has been challenged by the addition of different functional groups and shown to maintain chemoselectivity. Due to the broad reactivity with 1,2-methylenedioxybenzene derivatives, linear free energy correlations were determined and support a mechanism proceeding through diradicals analogous to arene-hydroxylation reactions using phthaloyl peroxide.
Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego , 9500 Gilman Drive, MC0756, La Jolla, California 92093, United States.|Department of Chemistry, University of Texas at Austin , Norman Hackerman Building, Austin, Texas 78701, United States.
Anders M
AM
Eliasen
Department of Chemistry, University of Texas at Austin , Norman Hackerman Building, Austin, Texas 78701, United States.
Mitchell
M
Christy
Department of Chemistry, University of Texas at Austin , Norman Hackerman Building, Austin, Texas 78701, United States.
Karin R
KR
Claussen
Department of Chemistry, University of Texas at Austin , Norman Hackerman Building, Austin, Texas 78701, United States.
Ronald
R
Besandre
Department of Chemistry, University of Texas at Austin , Norman Hackerman Building, Austin, Texas 78701, United States.
Randal P
RP
Thedford
Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego , 9500 Gilman Drive, MC0756, La Jolla, California 92093, United States.|Department of Chemistry, University of Texas at Austin , Norman Hackerman Building, Austin, Texas 78701, United States.
Dionicio
D
Siegel