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Synthesis 2014; 46(07): 909-916
DOI: 10.1055/s-0033-1338593
DOI: 10.1055/s-0033-1338593
paper
Cycloaddition of Styrenes as Phenylacetylene Substitutes on 2H-Pyran-2-ones and the Consequent Metal-Free Dehydrogenation: Case Study of Boscalid Derivatives
Further Information
Publication History
Received: 30 November 2013
Accepted after revision: 10 January 2014
Publication Date:
07 February 2014 (online)
Dedicated to Professor Bojan Verček, University of Ljubljana, Slovenia, on the occasion of his 65th birthday
Abstract
A novel use of styrenes as synthetic equivalents of phenylacetylenes is presented. To show its applicability, the method was tested for the preparation of a set of derivatives of boscalid, a commercially important fungicide. The strategy incorporates the Diels–Alder reaction of 3-acylamino-2H-pyran-2-ones with styrenes, followed by an efficient dehydrogenation step. The latter can be achieved either by the use of chloranil as the oxidant (under microwave irradiation) or by the application of activated charcoal Darco KB acting as a dehydrogenation catalyst (conventional heating).
Key words
cycloaddition - dehydrogenation - biaryls - heterogeneous catalysis - boscalid derivatives - heterocyclesSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
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The synthesis of 8a–c,l starts from appropriate compounds containing activated CH2 groups (i.e., 1,3-diketones, β-keto esters, etc.), C1-synthon (DMFDMA, trimethyl or triethyl orthoformate, etc.) and hippuric acid as described in: