Reactivity of methyl mandelate-Ti(IV)-enediolate: oxidative homocoupling versus aldol and direct Mannich-type syn-diastereoselective condensation.

作者信息

Clerici Angelo, Pastori Nadia, Porta Ombretta

机构信息

Dipartimento di Chimica, Materiali e Ingegneria Chimica Giulio Natta, Politecnico di Milano, Sezione Chimica, Via Mancinelli 7, 20131 Milano, Italy.

出版信息

J Org Chem. 2005 May 13;70(10):4174-6. doi: 10.1021/jo048279f.

[reaction: see text] Methyl mandelate undergoes quantitative oxidative homocoupling on treatment with TiCl4/amine at room temperature. In the presence of ArCHO, quantitative syn-diastereoselective aldol condensation takes over the dimerization, whereas exclusive Mannich-type syn-diastereoselective reaction is observed in the presence of both ArCHO and PhNH2. The subsequent reactions of the title intermediate do not depend on how it is generated.