Fluorinated Bifunctional Iminophosphorane Organocatalysis (F‐BIMP): Application to Nitro‐Mannich Reaction

ABSTRACT Excellent enantioselectivities have been obtained in the nitro‐Mannich addition of nitromethane on phosphinoyl ketimines catalyzed by chiral trifluoromethyl‐backbone‐based bifunctional iminophosphorane (F‐BIMP) organocatalysts. Fluorinated catalysts are synthesized straightfully from a common β‐amino alcohol precursor and their efficiency compared to the non‐fluorinated analogues. The scope of the transformation, including electron donating and withdrawing substrates, is described and the correlation between enantioselectivity and catalyst (thio)urea H‐bonds acidity is presented.