Synthetic Applications of the Pyrolysis of Meldrum’s Acid Derivatives

Abd El-Aal M Gaber; Hamish McNab

doi:10.1055/s-2001-18057

REVIEW

Synthetic Applications of the Pyrolysis of Meldrum’s Acid Derivatives

Abd El-Aal M. Gaber^a, Hamish McNab*^b
^a Chemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
^b Department of Chemistry, The University of Edinburgh, West Mains Road, Edinburgh, UK EH9 3JJ
Fax: +44(131)6504743; e-Mail: H.McNab@ed.ac.uk;

Abstract

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Abstract

The pyrolysis of Meldrum’s acid (2,2-dimethyl-1,3-dioxane-4,6-dione) 1 derivatives in solution and in the gas-phase takes place by loss of acetone and carbon dioxide to provide ketene intermediates. In particular, methylene Meldrum’s acid derivatives 7 often provide methyleneketenes 8, which act as substrates for internal hydrogen transfer leading to cyclisation reactions. The availability of versatile synthetic routes to 7 (in particular R = heteroatom) has led to the efficient preparation of a diverse range of cyclic compounds such as quinolinones, 3-hydroxythiophenes, naphthols, azepin-3(2H)-ones or pyrrolizin-3-ones initiated respectively by 1,3- 1,4- 1,5- 1,6- or 1,7-prototropic shifts. These reactions are discussed in the context of a rigorous understanding of the chemistry of the ketene intermediates involved. Most of the work was published in the period 1980-2000 but important references to earlier literature are also included.

1 Introduction
2 Meldrum’s Acid Derivatives
2.1 Cyclisations and Other Processes Preceded by a 1,3-Prototropic Shift
2.2 Cyclisations Preceded by a 1,4-Prototropic shift
2.3 Cyclisations Preceded by a 1,5-Prototropic Shift
2.4 Cyclisations Preceded by a 1,6-Prototropic Shift and Related Reactions
2.5 Cyclisations Preceded by a 1,7- Prototropic Shift
2.6 Cyclisations Involving Remote Prototropic Shifts
2.7 Eliminations and other Non-Cyclisation Processes
3 Coda

Key words

heterocycles - hydrogen transfer - pericyclic reactions - Meldrum’s acid - pyrolysis

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