Preparation of C ₂-Symmetric Biaryl Bisiminium Salts and Their Use as Organocatalysts for Asymmetric Epoxidation

Abstract

Two C ₂-symmetric bisiminium salt species containing biphenylazepinium units and derived from two chiral diamines were prepared and tested as organocatalysts for asymmetric epoxidation.

Key words

iminium - diamine - organocatalysis - epoxidation - biaryl

• References and Notes

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• 25 General Procedure for the Synthesis of 5H-Dibenzo[c,e]azepinium Salts from 2-[2-(Bromomethyl)phenyl]benzene Carbaldehyde and Primary Amines A solution of the amine (1 equiv) in EtOH (10 mL per gram of amine), was added dropwise to an ice-cooled solution of 2-[2-(bromomethyl)phenyl]benzene carbaldehyde (17, 1.1 equiv) in EtOH (10 mL per gram of 17). The reaction mixture was stirred overnight while attaining ambient temperature. Sodium tetra­phenylborate (1.1 equiv) dissolved in the minimum amount of MeCN was added in one portion to the reaction mixture and after stirring for 5 min, the organic solvents were removed under reduced pressure. EtOH was added to the residue, followed by few drops of H₂O. The resulting solid was collected by filtration and washed with additional EtOH followed by Et₂O. If no solid materializes after the addition of the H₂O the suspension is allowed to settle and the EtOH–H₂O phase is decanted. The gummy residue is macerated in hot EtOH or MeOH. The organic salt may then precipitate, and in rare cases it does so upon slow cooling of the hot alcoholic solution. If solubility problems do arise, small amounts of MeCN may be added during this process. For catalyst 19 Prepared according to the general procedure using (1S,2S)-diaminocyclohexane (10, 0.10 g, 0.88 mmol) and 2-[2-(bromomethyl)phenyl]benzene carbaldehyde (17, 0.51 g, 1.85 mmol, 2.1 equiv). The product 19 was isolated as yellow powder (0.51 g, 52%); mp 145–147 °C; [α]_D ²⁰ –170.2 (c 0.59, MeCN). IR (film): ν_max = 3052, 2933, 1639, 1597, 1552, 1480, 1445, 1425, 1332, 1265, 1208, 761, 731, 705 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆, 100 °C): δ = 1.77 (2 H, d, J = 12.0 Hz), 2.01 (2 H, d, J = 8.0 Hz), 2.30 (2 H, d, J = 8.0 Hz), 2.49–2.53 (2 H, m), 4.71 (2 H, d, J = 12.0 Hz), 5.06 (2 H, d, J = 12.0 Hz), 5.71 (2 H, s), 6.83 (8 H, t, J = 7.2 Hz), 6.97 (16 H, t, J = 7.2 Hz), 7.17–7.26 (18 H, m), 7.52 (4 H, br s), 7.73–7.79 (4 H, m), 7.87–8.06 (8 H, m). ¹³C NMR (100 MHz, DMSO-d ₆, 100 °C): δ = 24.0, 32.1, 55.0, 72.1, 121.9, 125.1, 125.6, 126.7, 127.0, 128.7, 129.0, 129.5, 130.4, 130.4, 133.8, 135.9, 136.2, 136.8, 141.5, 171.2. HRMS–FAB: m/z calcd for C₃₄H₃₂N₂ (cation): 468.2566; found: 468.2560
• 26 General Procedure for Epoxidation Reactions The alkene (1 equiv) and the catalyst (5 mol%) were dissolved in a mixture of MeCN and H₂O (10:1, 3 mL per mmol of alkene), and the mixture was cooled to 0 °C. A mixture of Oxone (2 equiv) and NaHCO₃ (5 equiv) was added as a solid in one portion to the mixture with vigorous stirring. The mixture was stirred at 0 °C until complete conversion of the alkene was observed by TLC. Et₂O (30 mL per mmol of alkene) was added, and the reaction mixture was filtered through a pad of mixed anhydrous MgSO₄ and NaHSO₃. The solvents were removed under reduced pressure, and the residue was purified using silica gel column chromatography using hexanes as the eluent.