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The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)–O Arylation

preprint
submitted on 14.02.2020 and posted on 18.02.2020 by Reginald Mills, John. J. Monteith, Sophie Rousseaux

The ability to understand and predict reactivity is highly important for the development of new reactions. In the context of Ni-catalyzed C(sp3)–O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp3)–O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active, and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.

Funding

Canada Foundation for Innovation - 19119, 35261

Canada Research Chair - 950-230935

Ministry of Research and Innovation

Natural Sciences and Engineering Research Council of Canada

University of Toronto

History

Email Address of Submitting Author

reggie.mills@mail.utoronto.ca

Institution

University of Toronto

Country

Canada

ORCID For Submitting Author

0000-0002-6329-2368

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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