Highly Chemoselective Stoichiometric
Alkylation of Ketones with Grignard Reagent Derived Zinc(II) Ate
Complexes

Manabu Hatano; Shinji Suzuki; Kazuaki Ishihara

doi:10.1055/s-0029-1219220

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Synlett 2010(2): 321-324
DOI: 10.1055/s-0029-1219220

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Highly Chemoselective Stoichiometric Alkylation of Ketones with Grignard Reagent Derived Zinc(II) Ate Complexes

Manabu Hatano^a, Shinji Suzuki^a, Kazuaki Ishihara*^a,b
^a Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan
^b Japan Science and Technology Agency (JST), CREST, Furo-cho, Chikusa, Nagoya 464-8603, Japan
Fax: +81(52)7893222; e-Mail: ishihara@cc.nagoya-u.ac.jp;

Further Information

Publication History

Received 5 October 2009
Publication Date:
04 January 2010 (online)

Abstract
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Abstract

A highly chemoselective alkylation of ketones with Grignard reagent derived stoichiometric zinc(II) ate complexes was developed. Zinc(II) ate complexes are readily prepared at room temperature within one hour in situ from ZnCl₂ and Grignard reagents without unstable alkyllithium reagents. The desired tertiary alcohols were obtained in much improved yields due to the minimization of background reactions with free Grignard reagents.

Key words

ate complex - Grignard reagent - ketone - tertiary alcohol - zinc

References

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9

In general, for aliphatic ketones, in sharp contrast to aromatic ketones, even stoichiometric zinc(II) ate reagents provided small improvements for selective alkylations.