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Synthesis 2005(13): 2234-2238  
DOI: 10.1055/s-2005-869952
PAPER
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Synthesis of α-Amido- and α-Carboxylic-β-Ketoesters

Søren Bertelsen, Martin Nielsen, Stephan Bachmann, Karl Anker Jørgensen*
Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark
e-Mail: kaj@chem.au.dk;
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Publication History

Received 20 February 2005
Publication Date:
20 June 2005 (online)

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Abstract

The rhodium-catalyzed N-H and O-H insertion of amides and carboxylic acids with α-diazo-β-ketoesters to give different α-amido- and α-carboxylic-β-ketoesters is presented. Investigations were carried out to establish an efficient N-H and O-H insertion reaction using a range of different amides and carboxylic acids for the synthesis of intermediates e.g. for receptor antagonists. The reactions were performed under mild conditions with 1 mol% of catalyst and the products were formed in good yields.

Keywords

amides - carboxylic acids - catalysis - diazo compounds - insertions - rhodium

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8

Pd(II), Co(II), Cu(I), Ni(II) and Rh(II) were tried. Besides Rh(II), no other metal gave satisfying results. No conversion was observed for Co(II) and Cu(I). Pd(II) and Ni(II) only afforded 10% yield in the initial studies, whereas Rh(II) gave roughly 70% yield.

13

No O-H insertion product could be isolated from entry 11 in Table [1] . Therefore the presence of O-H insertion product is believed to be due to the presence of an amide in the para position.