New Polymeric Disulfonimide for Heterogeneous Silicon Lewis Acid Catalysis

Abstract

A new heterogeneous polymeric disulfonimide was very easily synthesized from simple commercially available reagents. The new cost-effective catalytic material exhibited a tremendously enhanced reactivity in a benchmark Mukaiyama aldol reaction via silicon Lewis acid activation when compared with common acidic resins. Moreover, the reported polymeric disulfonimide exhibits outstanding robustness, as confirmed by its good thermal stability and excellent recyclability.

Key words

heterogeneous catalysis - disulfonimides - organocatalysis - silicon Lewis acid catalysis - ionomers

Publication History

Received: 31 May 2024

Accepted after revision: 19 June 2024

Accepted Manuscript online:
19 June 2024

Article published online:
09 July 2024

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• 15 Synthesis of poly-DSI 1: Polymer-bound sulfonyl chloride 2 (400 mg, 0.8 mmol, 1 equiv) and triethylamine (0.11 mL, 0.8 mmol, 1 equiv) dissolved in anhydrous THF (5 mL) was added to a 50-mL two-necked round-bottom flask purged with nitrogen. At 25 °C, 3 (95 mg, 0.8 mmol, 1.05 equiv) in anhydrous THF (1 mL) was added dropwise and the reaction was stirred at room temperature for 24 h. The solvent was removed in vacuo and the residue was washed with 1 M NaOH (10–15 mL) for 30 minutes, then centrifuged for 10 minutes at 3500 rpm. The solid polymer was then recovered and washed with HCl 2 M (10–15 mL) and water (10–15 mL), then recovered by centrifugation. Finally, the polymer was dried via azeotropic distillation with toluene. ¹H NMR (400 MHz, DMSO-d ₆, 303 K): δ = 7.28–7.21 (m, Ar C-H), 7.19–7.11 (m, Ar C-H), 3.14–2.95 (m, aliphatic CH₂). ¹⁹F NMR (376 MHz, DMSO-d ₆, 303 K): δ = –79.32. ATR-MIR: 1598 (ν(C-C)_arom), 1491, 1451 (δ(C-H)_aliph), 1396 (ν_asym(O=S=O)_N–bound), 1230 (ν_sym(CF₃)), 1195 (ν_asym(CF₃)), 1173 (ν_sym(O=S=O)_Cl–bound), 890 (ν(S-N)) cm^–1.
• 16 Poly-DSI 1 Catalysed Mukaiyama Aldol Reaction; General Procedure: Poly-DSI 1 and anhydrous CH₂Cl₂ were added to a 4-mL scintillation vial equipped with a magnetic bar. Aldehyde 5a–k (1 equiv) and nucleophile 6a–c (1.2–2.0 equiv) were then added and the reaction mixture was stirred at room temperature for the required time. The reaction was filtered on a plug of silica to remove the resin acid and the solvent was removed under vacuum. The crude material was purified by flash chromatography on SiO₂ (petroleum ether/ethyl acetate 9:1 v/v) to give the desired product.
• 17 Synthesis of Methyl 2,2-Dimethyl-3-phenyl-3-((trimethylsilyl)oxy)propanoate (7aa): Synthesized as described in the general procedure (ref. 16) for the poly-DSI 1 catalysed Mukaiyama aldol reaction using 1 (0.5 mg, 0.001 mmol), anhydrous CH₂Cl₂ (2 mL), benzaldehyde 5a (102 (L, 1 mmol), and nucleophile 6a (244 (L, 1.2 mmol). The reaction mixture was stirred at room temperature for 1 h. The desired product 7aa was obtained as a colourless oil (248 mg, 0.88 mmol, yield: 88%). ¹H NMR (400 MHz, CDCl₃, 303 K): δ = 7.31 (d, J = 3.7 Hz, 5 H), 5.02 (s, 1 H), 3.71 (s, 3 H), 1.17 (s, 3 H), 1.04 (s, 3 H), 0.00 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃, 303 K): δ = 177.3, 140.8, 127.8, 127.4, 79.2, 51.6, 49.1, 21.7, 19.2, –0.