FU ET AL.
5 of 6
RMgX ⋅LiCl with MeZnOMe, is able to convert aldehydes
into ketones at ambient temperature in high yields. The
key distinguishing feature of these reactions is that bime-
tallic alkoxyl organozincate intermediates were formed
which coordinated simultaneously with aldehyde sub-
strates and pivaldehyde, enabling the nucleophilic transfer
of R to aldehyde substrates and Oppenauer‐type transfer of
hydride to pivaldehyde in ‘one step’. This transformation
allows quick access to structurally diverse aryl as well as
heteroaryl, benzyl and alkyl ketones with broad substrate
scope and excellent functional group tolerance.
ACKNOWLEDGMENTS
We are grateful for financial support from the National
Natural Science Foundation of China (nos. 21762040,
21762039 and 21262030).
ORCID
REFERENCES
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4 | EXPERIMENTAL
4.1 | General Remarks
All the reactions were carried out under argon or nitro-
1
gen atmosphere. H NMR and 13C NMR spectra were
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4.2 | General Procedure for Preparation of
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Under argon or nitrogen atmosphere, alcohol (2.0 mmol)
in THF (4.0 ml) was added dropwise to 2.0 ml of
dialkylzinc reagent in toluene (1.0 M) in 30 min at 0 °C
and the reaction mixture was then stirred for another
30 min under the same conditions. Then Grignard
reagent RMgBr ⋅LiCl (2.5 mmol) in THF (5 ml) was added
carefully via a syringe and the reaction mixture was fur-
ther stirred at this temperature for 10 min.
4.3 | General Procedure for Reaction of
Organozinc Alkoxides with Aldehydes
To the organozinc alkoxide prepared as described in Sec-
tion 4.2 was added a solution of substrate aldehyde
(2.0 mmol) and pivaldehyde (0.34 g, 4.0 mmol, 0.43 ml)
in THF (10 ml) in an ice–water bath. After the reaction
mixture was stirred at room temperature for 2 h, the reac-
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with brine (10 ml). The water phase was extracted with
ethyl acetate (2 × 10 ml). The organic phase was com-
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pressure. Ketones were obtained by column chromatogra-
phy on silica gel using petroleum–ethyl acetate as an
eluent.
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