Synthesis 2017; 49(03): 667-676
DOI: 10.1055/s-0036-1588078
paper
© Georg Thieme Verlag Stuttgart · New York

One-Pot Synthesis of α-Ylidene δ-Lactones from Functionalized Allylic Bromides in a Water–Isopropanol Medium

Misael Ferreira
a   Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC 88040-900, Brazil   Email: marcus.sa@ufsc.br
,
Tula B. Bisol
b   Instituto Federal de Santa Catarina, Campus Florianópolis, Florianópolis, SC 88020-300, Brazil
,
Henrique P. da Conceição
a   Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC 88040-900, Brazil   Email: marcus.sa@ufsc.br
,
Theo V. C. Russo
a   Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC 88040-900, Brazil   Email: marcus.sa@ufsc.br
,
Adailton J. Bortoluzzi
a   Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC 88040-900, Brazil   Email: marcus.sa@ufsc.br
,
Marcus M. Sá*
a   Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC 88040-900, Brazil   Email: marcus.sa@ufsc.br
› Author Affiliations
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Publication History

Received: 26 July 2016

Accepted after revision: 06 September 2016

Publication Date:
13 October 2016 (online)


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Abstract

The one-pot microwave-assisted synthesis of a series of α-ylidene δ-lactones from (Z)-2-(bromomethyl)-2-alkenoates (derived from Morita–Baylis–Hillman reaction) in an aqueous environment is reported. The protocol includes regioselective base-mediated allylation of ethyl acetoacetate with (Z)-2-(bromomethyl)-2-alkenoates followed by decarboxylative hydrolysis, carbonyl reduction of the keto carboxylate intermediate, and acid-mediated cyclization of the resulting δ-hydroxy acid to furnish the α-ylidene δ-lactones with good overall yields. The synthesis was also performed in the stepwise mode, which allowed the isolation and full characterization of each intermediate involved in the one-pot method. The main features of this efficient transformation include the fast reaction rates, the use of a benign aqueous medium, the use of inexpensive and readily available reagents, the production of nearly innocuous residues, and the requirement for a single work-up and purification stage at the end of the process.

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