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

• Published in: Applied organometallic chemistry 2023-12, Vol.37 (12), p.n/a
• Main Authors: Cruz, Tiago F. C., Figueira, Cláudia A., Gomes, Pedro T.
• Format: Article
• Language: English
• Subjects: 2‐iminopyrrolyl ligands; Aldehydes; Chemical analysis; Chemistry; Copper; copper(I) complexes; Hydroboration; Ligands; NMR spectroscopy; pinacolborane; Potassium salts; Single crystals; Substitutes; X-ray diffraction; α,β‐unsaturated aldehydes
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.7309

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 ion 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. Eight new copper(I) complexes of bulky 5‐substituted‐2‐iminopyrrolyl ligands were synthesized and characterized. The new copper complexes catalyzed the one‐step 1,4‐hydroboration of α,β‐unsaturated aldehydes and the 1,2‐hydroboration of additional aldehydes with pinacolborane.