Rhodium-Catalyzed Regioselective 3-Fluoroallylic Cyanation

A rhodium catalyzed allylic cyanation of 3-fluoroallylic trifluoroacetates with TMSCN and a bulky phosphite ligand gives 3-fluoroallylic nitriles with a good substrate scope and high Z/E-selectivity. For dialkylated substrates the fluorine substituent controls the regioselectivity in favor of the distal product. For the stereoselectivity of the allylic cyanation selected scalemic substrates showed inversion of the stereocenter and some or no stereoerosion.

Automated summary

The rhodium-catalyzed allylic cyanation of 3-fluoroallylic trifluoroacetates with TMSCN and a bulky phosphite ligand efficiently produces 3-fluoroallylic nitriles with a wide substrate scope and high Z/E-selectivity. The fluorine substituent controls the regioselectivity in favor of the distal product for dialkylated substrates. Selected scalemic substrates show inversion of stereocenter and minimal or no stereoerosion in the stereoselectivity of allylic cyanation.