Takahashi R,
Hu A,
Gao P,
Gao Y,
Pang Y,
Seo T,
Jiang J,
Maeda S,
Takaya H,
Kubota K,
*,
Ito H.
*
Hokkaido University, Sapporo, Japan
Mechanochemical Synthesis of Magnesium-Based Carbon Nucleophiles in Air and Their
Use in Organic Synthesis.
Nat. Commun. 2021;
12
DOI:
10.1038/s41467-021-26962-w
Key words
ball mill - carbon nucleophiles - Grignard reagents - mechanochemical synthesis
Significance
A mechanochemical approach for the generation of Grignard reagents using a ball mill
is presented. The solvent-free, in-air generation of these carbon nucleophiles and
their nucleophilic addition to electrophiles opens a straightforward way to conduct
a classic reaction. This method can also be applied to Kumada–Tamao–Corriu couplings
and copper-catalyzed conjugate additions.
Comment
Addition of various mechanochemically prepared Grignard regents to aldehydes or ketones
gives the corresponding alcohols in good to excellent yield. Even solid arylbromides
with low solubility can be transformed into the corresponding Grignard reagents where
the classic approach fails. Only 3.0–6.0 equivalents of a coordinating ether solvent
are required for the reaction to occur.
