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Synthesis 2011(21): 3482-3490  
DOI: 10.1055/s-0030-1260230
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Phosphonium Salt Catalyzed Addition of Diethylzinc to Aldehydes

Thomas Werner*, Abdol Majid Riahi, Heiko Schramm
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
Fax: +49(381)128151326; e-Mail: thomas.werner@catalysis.de;
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Publication History

Received 9 June 2011
Publication Date:
26 September 2011 (online)

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Abstract

The addition of diethylzinc to aromatic, heteroaromatic, and aliphatic aldehydes at room temperature is efficiently catalyzed by 1-7 mol% tetrabutylphosphonium chloride. The corresponding addition products are obtained in good to excellent yields of up to 99%. Moreover, polymer bond phosphonium salts can be used to catalyze this reaction with excellent recovery of the polymer bond catalyst up to three cycles. The application of chiral bifunctional phosphonium salts revealed a remarkable counter anion effect. Changing the anion, the activity of the tetrabutylphosphonium salt decreased in the order Cl- > Br- > I- ≈ TsO- > BF4 - ≈ PF6 -. However, the nature of the cation had also significant influence. Tetraalkyl­ammonium chlorides showed similar activity compared to phosphonium chlorides, while alkaline metal chlorides proved to be considerably less active.

Key words

catalysis - phosphonium salt - addition - diethylzinc - aldehydes

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[(2S)-3-Hydroxy-2-methylpropyl](triphenyl)phosphonium bromide (9) was purchased from Sigma-Aldrich.