Studies on the Stability of Cycloprop-2-ene Carboxylate Dianions and Reactions with Electrophiles
Authors:
- 14 October 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 73 (21) , 8474-8478
Abstract
Dianions are generated from alkyllithium reagents and cycloprop-2-ene carboxylic acids, and these dianions can be functionalized by electrophiles at the vinylic position. In a previous report, we described that such dianions could be generated and reacted with electrophiles in Et2O or THF. Upon further study, it was found that there were reproducibility issues for those reactions that were carried out in Et2O. Working under the assumption that an impurity may have promoted these reactions, a detailed study was undertaken to determine the effect of variables on the generation, stability, and reactivity of cycloprop-2-ene carboxylate dianions. It has been found that certain additives can have a substantial effect on the chemistry of cycloprop-2-ene carboxylate dianions. In particular, it was determined that amine N-oxide additives have a beneficial effect both on the stability of cycloprop-2-ene carboxylate dianions and on the rates that such dianions undergo alkylation. Conditions for reacting dianions with a broad range of electrophiles are described.Keywords
This publication has 34 references indexed in Scilit:
- Synthesis and Application of Alkenylstannanes Derived from Base-Sensitive CyclopropenesOrganic Letters, 2008
- A New Chiral Rh(II) Catalyst for Enantioselective [2 + 1]-Cycloaddition. Mechanistic Implications and ApplicationsJournal of the American Chemical Society, 2004
- Novel Organogermanium Compounds via Metalation of 3-Trimethylsilyl-3-ethoxycarbonylcyclopropene DerivativesOrganometallics, 2004
- A Reactivity/Affinity Switch for Parallel Kinetic Resolution: α-Amino Acid Quasienantiomers and the Resolution of Cyclopropene Carboxylic AcidsJournal of the American Chemical Society, 2004
- Lithiation/silylation of ethyl 2-alkyl-1-trimethylsilylcycloprop-2-ene-1-carboxylate. Experimental and computational studyNew Journal of Chemistry, 2003
- Chemoselectivity and enantiocontrol in catalytic intramolecular metal carbene reactions of diazo acetates linked to reactive functional groups by naphthalene-1,8-dimethanolChemical Communications, 1999
- Quinuclidine N-oxide: a potential replacement for HMPAChemical Communications, 1999
- Effective Uses of Dirhodium(II) Tetrakis[methyl 2-oxopyrrolidine-5(R or S)-carboxylate] for Highly Enantioselective Intermolecular Cyclopropenation ReactionsJournal of the American Chemical Society, 1994
- Functionalised cyclopropenes as synthetic intermediates1988
- Chemistry of cyclopropene III: Synthesis of mono‐ and dialkylated cyclopropenesRecueil des Travaux Chimiques des Pays-Bas, 1973