Anti-Markovnikov N−H and O−H Additions to Electron-Deficient Olefins Catalyzed by Well-Defined Cu(I) Anilido, Ethoxide, and Phenoxide Systems

The monomeric Cu(I) complexes (IPr)Cu(Z) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, Z = NHPh, OEt, or OPh) react with YH (Y = PhNH, PhCH2NH, EtO, or PhO) to catalytically add Y-H bonds across the C=C bond of electron-deficient olefins to yield anti-Markovnikov organic products. Catalytic activity has been observed for olefins CH2C(H)(X) with X = CN, C(O)Me, or CO2Me as well as crotononitrile. Preliminary studies implicate an intermediate in which the C-Y bond forms through a nucleophilic addition pathway.