Thiourea-based iminophosphorane (BIMP) organocatalysts featuring SPhos- or BIDIME phosphine units have been developed and successfully applied in the asymmetric addition of nitromethane to N-Boc-protected trifluoromethyl aryl ketimines. α-Trifluoromethyl β-nitroamines were obtained 40–82% isolated yields 80–95% enantioselectivities. A careful evaluation catalytic activity BIMPs indicates that c...