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

18 February 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

Cyclopropanol
Cyclopropane
Redox-Active
Negishi Arylation
Catalysis
Nickel
Redox-active leaving group
Radical
Cross-coupling
Alcohol

Supplementary materials

Title
Description
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Title
Rousseaux - Redox-Active Cyclopropanol - SI 1
Description
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Rousseaux - Redox-Active Cyclopropanol - SI 2
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Rousseaux - Redox-Active Cyclopropanol - TOC
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