Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates 英文参考文献.docVIP

Molecules 2008, 13, 1303-1311 manuscripts; DOI: 10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /molecules Communication Unusual Regioselectivity in the Opening of Epoxides by Carboxylic Acid Enediolates Luis R. Domingo, Salvador Gil, Margarita Parra* and José Segura Department of Organic Chemistry, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Spain. Fax +34(9 E-mails: Salvador.gil@uv.es; jofranse@uv.es; Luis.Domingo@uv.es * Author to whom correspondence should be addressed; E-mail: Margarita.Parra@uv.es Received: 29 May 2008; in revised form: 5 June 2008 / Accepted: 6 June 2008 / Published: 9 June 2008 Abstract: Addition of carboxylic acid dianions appears to be a potential alternative to the use of aluminium enolates for nucleophilic ring opening of epoxides. These conditions require the use of a sub-stoichiometric amount of amine (10% mol) for dianion generation and the previous activation of the epoxide with LiCl. Yields are good, with high regioselectivity, but the use of styrene oxide led, unexpectedly, to a mixture resulting from the attack on both the primary and secondary carbon atoms. Generally, a low diastereoselectivity is seen on attack at the primary center, however only one diastereoisomer was obtained from attack to the secondary carbon of the styrene oxide. Keywords: Lactones, lithium chloride, nucleophilic addition, regioselectivity, diastereoselectivity. Introduction Epoxides have been recognized among the most versatile compounds in organic synthesis, not only as final products [1] but as key intermediates for further manipulations. Accordingly, new synthetic developments are continuously being published [2]. Due to its high ring strain (around 27 Kcal/mol) its ring-opening, particularly with carbon-based nucleophiles, is a highly valuable synthetic strategy  Molecules 2008, 13 1304 [3]. The usefulness of epox