Dearomatization Reactions Using Phthaloyl Peroxide
Anders M Eliasen1,2, Mitchell Christy2, Karin R Claussen2
1Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego , 9500 Gilman Drive, MC0756, La Jolla, California 92093, United States.
Chemists developed a novel oxidative dearomatization reaction using phthaloyl peroxide to selectively add two oxygen-carbon bonds to aromatic compounds. This reaction is highly selective and proceeds only once, even with various functional groups present.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Oxidative dearomatization is a key transformation in organic synthesis.
- Developing selective methods for installing oxygen functionalities into aromatic systems remains a challenge.
Purpose of the Study:
- To develop a novel oxidative dearomatization reaction for aromatic precursors.
- To achieve chemoselective installation of two oxygen-carbon bonds.
- To investigate the reaction mechanism and scope.
Main Methods:
- Utilized phthaloyl peroxide as the oxidant.
- Employed various aromatic precursors with diverse functional groups.
- Performed linear free energy correlations to elucidate the mechanism.
Main Results:
- Developed a new oxidative dearomatization reaction with phthaloyl peroxide.
- Achieved chemoselective installation of two oxygen-carbon bonds.
- Demonstrated reaction selectivity with various functional groups and 1,2-methylenedioxybenzene derivatives.
- Supported a diradical mechanism analogous to arene-hydroxylation.
Conclusions:
- Phthaloyl peroxide enables a selective oxidative dearomatization of aromatic precursors.
- The reaction proceeds via a single oxidation step, forming 1,3-cyclohexadienes.
- The mechanism involves diradicals, similar to known arene-hydroxylation pathways.
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