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. 2020 Jun 19;85(12):7848-7862.
doi: 10.1021/acs.joc.0c00481. Epub 2020 May 28.

Evidence against Single-Electron Transfer in the Additions of Most Organomagnesium Reagents to Carbonyl Compounds

Nicole D Bartolo  1 , K A Woerpel  1
Affiliations

Evidence against Single-Electron Transfer in the Additions of Most Organomagnesium Reagents to Carbonyl Compounds

Nicole D Bartolo et al. J Org Chem. .

Abstract

A radical clock system was developed to investigate single-electron transfer (SET) in the reactions of organomagnesium reagents with carbonyl compounds. The fluorenylcyclopropyl radical clock was selected because it is the fastest known radical clock. Additions of Grignard reagents to aldehydes or methyl ketones provided no evidence for ring-opened products that would indicate reaction through SET. Additions of some Grignard reagents to aromatic ketones, however, resulted in the formation of ring-opened products, suggesting SET.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Synthesis of radical clock probes
Scheme 2.
Scheme 2.
Possible ring-opened and ring-closed products that correspond to ions detected by LC-MS (ESI) in the unpurified reaction mixture of the addition of t-Bu–MgCl to ketone 7
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