Improved synthesis of and nucleophilic addition to 2-formyl-2-cyclohexenone

• Published in: Tetrahedron letters Vol. 56; no. 2; pp. 386 - 389
• Main Authors: Adary, Elan M., Chang, Chih-wei, D’ Auria, Damian T., Nguyen, Phuc M., Polewacz, Klaudyna, Reinicke, Justin A., Seo, Hannah, Berger, Gideon O.
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 08.01.2015; Elsevier
• Subjects: 2-Formyl-2-cycloalkenone; 2-Formyl-2-cyclohexenone; Chemistry; Chemistry, Organic; Conjugate addition; Conjugates; Dimethylmalonate; Homology; Michael addition; Nucleophiles; Physical Sciences; Purity; Science & Technology; Synthesis (chemistry); Tetrahedrons; 2-Formyl-2-cycloalkenone; Michael addition; Conjugate addition; Dimethylmalonate; 2-Formyl-2-cyclohexenone; ANNULATION; BETA-DICARBONYL COMPOUNDS; dimethylmalonate; 2-formyl-2-cycloalkenone; Michael Addition; conjugate addition; 2-formyl-2-cyclohexenone
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2014.11.100

[Display omitted] A preparation of 2-formyl-2-cyclohexenone in nearly quantitative yield and purity of approximately 95% is described. It is scalable and has been extended to the synthesis of the 5- and 7-membered ring homologs with comparable yields. Conditions have also been developed for the successful conjugate addition of dimethylmalonate to 2-formyl-2-cyclohexenone, in good and scalable yield (60%). This result has been extended to 5 other nucleophile classes, and the dimethylmalonate conjugate addition has been demonstrated with 2-formyl-2-cyclopentenone and 2-formyl-2-cycloheptenone.