Hydro(trispyrazolyl)borato-Ruthenium(II) Diphosphinoamino Complex-Catalyzed Addition of β-Diketones to 1-Alkynes and Anti-Markovnikov Addition of Secondary Amines to Aromatic 1-Alkynes

The hydro(trispyrazolyl)borato-ruthenium(II) diphosphinoamino complex TpRu[4CF(3)C(6)H(4)N(PPh2)(2)] (OTf) (I) [Tp=hydro(trispyrazolyl)borate] catalyzes the Markovnikov addition of beta-diketones to unactivated 1-alkynes in good to excellent yields. The reaction proceeds under solvent-free can be reduced down to 0.4 mol%. Complex I (1 mol%) also catalyzes the addition of secondary amines to aromatic terminal alkynes, unusual anti-Markovnikov products are exclusively formed.