Highly selective reaction of alpha-halo-alpha,beta-unsaturated esters with ketones or aldehydes promoted by SmI2: an efficient alternative access to Baylis-Hillman adducts

José M Concellón; Mónica Huerta

doi:10.1021/jo0504969

Highly selective reaction of alpha-halo-alpha,beta-unsaturated esters with ketones or aldehydes promoted by SmI2: an efficient alternative access to Baylis-Hillman adducts

J Org Chem. 2005 Jun 10;70(12):4714-9. doi: 10.1021/jo0504969.

Authors

José M Concellón¹, Mónica Huerta

Affiliation

¹ Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, C. Julián Clavería 8, 33071 Oviedo, Spain. jmcg@fq.uniovi.es

PMID: 15932309
DOI: 10.1021/jo0504969

Abstract

A samarium diiodide promoted addition of aromatic or aliphatic beta-substituted-alpha-halo-alpha,beta-unsaturated esters 1 or 3 to both ketones (in THF) and aldehydes (in acetonitrile) led to (Z)-2-(1-hydroxyalkyl)-2,3-alkenoates 2 and 4 in good yields and very high stereoselectivity. This method constitutes an efficient and valuable alternative to the synthesis of Baylis-Hillman adducts. A mechanism is proposed to explain this transformation.