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Synthesis 2002(3): 0317-0319
DOI: 10.1055/s-2002-20027
SHORTPAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of β-Keto Esters by Carbonylation of Halomethylketones

A. L. Lapidus*a, O. L. Eliseeva, T. N. Bondarenkoa, O. E. Sizana, A. G. Ostapenkoa, I. P. Beletskayab
a N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russian Federation
Fax: +7(95)1355303; e-Mail: oleg@ioc.ac.ru;
b Department of Chemistry, Moscow State University, Moscow, Russian Federation
Fax: +7(95)9381844; e-Mail: beletska@org.chem.msu.su;
Further Information

Publication History

Received 26 October 2001
Publication Date:
28 July 2004 (online)

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Abstract

A number of β-keto esters were synthesized by Pd-catalyzed carbonylation of halomethylketones in the presence of tributylamine in 68-86% yields. The reaction is completed in 2 hours at 110 °C and 10 bar CO pressure. Chloromethylketones are carbonylated selectively while 2-bromoacetophenone is partly reduced to acetophenone as a byproduct. The reaction can be carried out at atmospheric pressure though the rate stays low. The reaction mechanism is discussed.

Key words

halomethylketones - β-keto esters - carbonylation - palladium - catalysis

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