nucleophilic benzoylation using a mandelic acid dioxolanone as a synthetic equivalent of the benzoyl carbanion. oxidative decarboxylation of α-hydroxyacids亲核的苯甲酰化使用扁桃酸dioxolanone作为合成的苯甲酰负碳离子。.pdfVIP

Molecules 2004, 9, 365-372 molecules ISSN 1420-3049 Nucleophilic Benzoylation Using a Mandelic Acid Dioxolanone as a Synthetic Equivalent of the Benzoyl Carbanion. Oxidative Decarboxylation of α-Hydroxyacids Gonzalo Blay, Isabel Fernández, Belén Monje and José R. Pedro* Departament de Química Orgànica, Facultat de Química, Universitat de València, E-46100 Burjassot(València), Spain. Tel. +34-963544329, Fax +34-963544328. * Author to whom correspondence should be addressed; e-mail: Jose.R.Pedro@uv.es Received: 5 March 2004 / Accepted: 18 March 2004 / Published: 30 April 2004 Abstract: The synthesis of alkyl aryl ketones using a mandelic acid dioxolanone as a synthetic equivalent (Umpolung) of the benzoyl carbanion is reported. The methodology involves alkylation of the mandelic acid dioxolanone, hydrolysis of the dioxolanone moiety in the alkylated products and oxidative decarboxylation of the resulting α-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co (III) complex in the presence of pivalaldehyde under very mild conditions. Keywords: Alkylation, dioxolanone, decarboxylation, catalysts, cobalt, Umpolung. Introduction We have recently reported the use of methyl mandelate as a masked d1-synthon for nucleophilic benzoylation (Umpolung) of the carbonyl group [1] in a synthesis of aryl alkyl ketones, which involves alkylation of methyl mandelate, hydrolysis of the ester group in the alkylated products and oxidative decarboxylation of the resulting α-hyd