Activation of Chiral (Salen)TiCl2 Complex by Phosphorane for the Highly Enantioselective Cyanation of Nitroolefins

• DOI: 10.1021/acs.orglett.0c00612
• Publication Date: 2020-02-27T16:59:25Z
• Authors: Chen Chen; Wen-Biao Wu; Yan-Hong Li; Qiu-Hua Zhao; Jin-Sheng Yu; Jian Zhou
• Keywords: Phosphorane; Cyanation

We report that phosphorane can activate (salen)TiCl2 complex to achieve unprecedented excellent enantioselectivity and a broad substrate scope in the cyanation of nitroolefins. Our cyanating reagent Me2(CH2Cl)SiCN proves be more active than TMSCN this reaction, allowing 11 β-aliphatic nitrolefins 12 β-CF3 nitroolefins (either β-aryl or aliphatic) work well give corresponding tertiary quaternary β-nitronitriles with high enantioselectivity.