Dimethyl malonate/LHMDS system as a new protocol for generating methyl formate anion (−COOMe) in the condensed-phase. Issue 15 (13th April 2016)

• Record Type: Journal Article
• Authors: Di Bussolo, Valeria; Princiotto, Salvatore; Martinelli, Elisa; Bordoni, Vittorio; Crotti, Paolo
• Is Part Of: Tetrahedron letters. Volume 57:Issue 15(2016)
• Page Start: 1644
• Page End: 1647
• Publication Date: 2016-04-13
• Subjects: Methyl formate anion -- Methoxycarbonyl anion -- Dimethyl malonate -- Condensed-phase -- Nucleophilic substitution; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2016.02.090
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: A new protocol for the formation of methyl formate anion in the condensed-phase is given. The protocol is based on the treatment of dimethyl malonate with LHMDS. A rationalization based on a double deprotonation of dimethyl malonate is proposed. Abstract: The treatment of dimethyl malonate with LHMDS in anhydrous THF (condensed-phase) generates, in addition to the expected corresponding lithium enolate, methyl formate anion (or methoxycarbonyl anion, − COOMe) which can react with several electrophiles to give corresponding methoxycarbonyl derivatives by nucleophilic substitution reaction.