{Reference Type}: Journal Article
{Title}: Spectroscopic and Computational Study of the Organocatalytic Umpolung of Bromocations: An Accelerated Stereoselective Dibromination Protocol.
{Author}: Panda J;Sahoo J;Dutta J;Biswal HS;Sahoo G;
{Journal}: Chemistry
{Volume}: 29
{Issue}: 45
{Year}: 2023 Aug 10
{Factor}: 5.02
{DOI}: 10.1002/chem.202300675
{Abstract}: Herein, organocatalytically achieved polarity reversal of cationic bromine is presented. The proven bromocation source N-bromosuccinimide (NBS) was converted to a superior bromoanion reagent by H/Br exchange with a secondary amine, substantiated with spectroscopic and computational evidence. The concept has further been used in a successfully accelerated organocatalyzed dibromination of olefins in a non-hazardous, commercially viable process with a wide range of substrate scope. The reactivity of key entities observed through NMR kinetics and reaction acceleration using only 10 mol % of catalyst account for its major success. The nucleophilicity of the bromoanion was found to be superior in comparison to other nucleophiles such as MeOH and H2 O also the protocol dominates over the competing allylic bromination reaction.