DOI: 10.1002/aoc.7309 ISSN: 0268-2605

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

Tiago F. C. Cruz, Cláudia A. Figueira, Pedro T. Gomes
  • Inorganic Chemistry
  • General Chemistry

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{κNN'‐5‐R‐NC4H2‐2‐C(H) = N(2,6‐iPr2C6H3)}]2 (D1D6) with triphenylphosphine (PPh3); (2) the reaction of the respective 5‐R‐2‐iminopyrrolyl potassium salts (KL1KL3 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 57 displayed tetrahedral (for 1) and trigonal planar (for 3 and 57) 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.

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