One-pot Hofmann elimination–transesterification/amidation reactions on REM resin using perfluorous solvents

The incorporation of 2,2,2-trifluoroethanol esters into substrates for the REM resin synthesis of 3° amines allows a one-pot Hofmann elimination/transesterification protocol to be performed. In this way α-amino acid esters and amides were synthesised by adding alcohols or 1° amines to the Hofmann elimination mixture. The excess of nucleophile required to drive the transesterification or amidation to completion was found to be considerably lower when perfluorous solvents were used to accelerate the reaction (FAST effect).