Hydroboration of aldehydes with pinacolborane catalyzed by bulky 2‐iminopyrrolyl copper(I) triphenylphosphine complexes

Eight new copper(I) triphenylphosphine complexes of bulky 5‐substituted‐2‐iminopyrrolyl ligands [Cu{κ²N,N′‐5‐R‐NC₄H₂–2‐C(H) = N(2,6‐iPr₂C₆H₃)}(PPh₃)_n] (for n = 2: R = 2,6‐Me₂C₆H₃ (1), 3,5‐(CF₃)₂C₆H₃ (2); for n = 1: R = 2,4,6‐iPr₃C₆H₂ (3), CPh₃ (4), 2,6‐(OMe)₂C₆H₃ (5), 2,4,6‐Ph₃C₆H₂ (6), 2,6‐Me₂C₆H₃ (7), 3,5‐(CF₃)₂C₆H₃ (8)) are presently reported. The complexes were prepared in good yields by: (1) the reaction of the previously reported binuclear complexes [Cu{κN,κN'‐5‐R‐NC₄H₂‐2‐C(H) = N(2,6‐iPr₂C₆H₃)}]₂ (D1–D6) with triphenylphosphine (PPh₃); (2) the reaction of the respective 5‐R‐2‐iminopyrrolyl potassium salts (KL1–KL3 and KL5) and [Cu(NCMe)₂(PPh₃)₂]BF₄; or (3) the abstraction of one PPh₃ ligand present in complexes 1 and 2 with one equivalent of tris(pentafluorophenyl)borane (only for complexes 7 and 8, respectively). All complexes were characterized by NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X‐ray diffraction. The single crystal X‐ray diffraction structures of 1, 3, and 5–7 displayed tetrahedral (for 1) and trigonal planar (for 3 and 5–7) coordination geometries. All complexes catalyzed the 1,4‐hydroboration of some α,β‐unsaturated (E)‐2‐enals with pinacolborane (HBPin), with 1,4:1,2‐addition selectivities as high as 29:1, the maximum turnover frequencies being equal to 9.9 min⁻¹, and the 1,4‐hydroboration selectivity being favored by increasing steric protection of the 5‐substituted‐2‐iminopyrrolyl scaffold. Additionally, these complexes also catalyzed the hydroboration of an array of other aldehydes, reaching TOFs as high as 9.9 min⁻¹. A combination of control experiments suggests that the catalyst system operates via a non‐classical copper‐hydride outer sphere route.