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

Abstract

Abstract The hydro(trispyrazolyl)borato‐ruthenium(II) diphosphinoamino complex TpRu[4‐CF 3 C 6 H 4 N(PPh 2 ) 2 ](OTf) ( I ) [Tp=hydro(trispyrazolyl)borate] catalyzes the Markovnikov addition of β‐diketones to unactivated 1‐alkynes in good to excellent yields. The reaction proceeds under solvent‐free and additive‐free conditions and the catalyst loading 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.