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Synthesis 2004(15): 2560-2566  
DOI: 10.1055/s-2004-831235
PAPER
© Georg Thieme Verlag Stuttgart · New York

α-Methylene-β-trichloroacetylamino Alkanoates from Trichloroacetimidates of the Baylis-Hillman Adducts

Roberta Galeazzi, Gianluca Martelli, Mario Orena*, Samuele Rinaldi
Dipartimento di Scienze dei Materiali e della Terra, Università Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy
Fax: +39(071)2204714; e-Mail: m.orena@univpm.it;
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Publication History

Received 11 June 2004
Publication Date:
22 September 2004 (online)

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Abstract

The Baylis-Hillman adducts 1 were treated with a large amount of CCl3CN in the presence of DBU without solvent to give in good yield the corresponding trichloroacetimidates 5 which by thermal [3.3]sigmatropic rearrangement were converted into the corresponding (E)-2-trichloroacetylaminomethyl-2-propenoates 6, exclusively. On the contrary, when compounds 5 were treated with a catalytic amount of DABCO in dichloromethane, 2-methylene-3-trichloroacetylamino esters 7 were obtained in good yield. Both 5a and 7a underwent iodocyclization, to give a cyclic intermediate precursor of a polyfunctionalized sequence, and the differences in stereoselectivity were in agreement with computational results.

Key words

amino acids - amides - rearrangement - cyclization - stereoselectivity

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12

It is worth mentioning that molecular mechanics calculations carried out for all compounds 5 indicate the presence of a number of conformers within a short energy range. Rotameric mixtures are evidenced by the 1H NMR spectra of the ethyl derivatives 5b,d,f,k, where a multiplet or a double quartet collapsing at 50 °C into a quartet takes place for the ethyl quartet.