Chloroform as a Hydrogen Atom Donor in Barton Reductive Decarboxylation Reactions
Citations Over TimeTop 13% of 2013 papers
Abstract
The utility of chloroform as both a solvent and a hydrogen atom donor in Barton reductive decarboxylation of a range of carboxylic acids was recently demonstrated (Ko, E. J. et al. Org. Lett. 2011, 13, 1944). In the present work, a combination of electronic structure calculations, direct dynamics calculations, and experimental studies was carried out to investigate how chloroform acts as a hydrogen atom donor in Barton reductive decarboxylations and to determine the scope of this process. The results from this study show that hydrogen atom transfer from chloroform occurs directly under kinetic control and is aided by a combination of polar effects and quantum mechanical tunneling. Chloroform acts as an effective hydrogen atom donor for primary, secondary, and tertiary alkyl radicals, although significant chlorination was also observed with unstrained tertiary carboxylic acids.
Related Papers
- → A NOVEL DECARBOXYLATION OF α-AMINO ACIDS. A FACILE METHOD OF DECARBOXYLATION BY THE USE OF 2-CYCLOHEXEN-1-ONE AS A CATALYST(1986)65 cited
- → Studies in decarboxylation. Part 15. The effect of 3-substitution on the rate of decarboxylation of βγ-unsaturated acids(1982)6 cited
- → ChemInform Abstract: A Novel Decarboxylation of α‐Amino Acids. A Facile Method of Decarboxylation by the Use of 2‐Cyclohexen‐1‐one as a Catalyst.(1986)2 cited
- → Barton Decarboxylation(2010)1 cited
- → A novel method for monitoring of Δ 9 -tetrahydrocannabinolic acid and cannabidiolic acid thermal decarboxylation reactions in cannabis plant(2023)