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Synlett 2010(2): 321-324  
DOI: 10.1055/s-0029-1219220
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© Georg Thieme Verlag Stuttgart ˙ New York

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

Manabu Hatanoa, Shinji Suzukia, 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;
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Publication History

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

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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

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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.