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DOI: 10.1055/a-2349-1863
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New Polymeric Disulfonimide for Heterogeneous Silicon Lewis Acid Catalysis

Giuliana Giorgianni‡
a   Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy
,
Maria Edith Casacchia‡
a   Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy
b   IUSS Scuola Universitaria Superiore di Pavia, Palazzo del Broletto, Piazza della Vittoria, 15 27100, Pavia, Italy
,
Pier Carlo Ricci
c   Dipartimento di Fisica, Università di Cagliari, sp 8, km 0.700, 09042 Monserrato, Italy
,
Simone Di Muzio
a   Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy
d   Istituto dei Sistemi Complessi, ISC-CNR U.O.S. Sapienza, P.le A. Moro 5, 00185 Rome, Italy
,
Andrea Lazzarini 
a   Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy
,
Armando Carlone 
a   Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy
,
Fabio Pesciaioli  ∗
a   Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy
› Author AffiliationsG.G. is grateful to the Ministero dell’Università e della Ricerca (PON-DOT13OV2OC) for an industrial PhD fellowship. F.P. thanks the Ministero dell’Università e della Ricerca (PON–AIM1842894, CUP–E18D19000560001) and the Royal Society of Chemistry Research fund (R20-3636) for funding this research. M.E.C. thanks the support of the Italian national inter-university PhD course in Sustainable Development and Climate Change. A.C. acknowledges funding by the European Union - NextGenerationEU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem grant ECS00000041 - VITALITY - CUP E13C22001060006.
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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2349-1863.
  • Supporting Information


Publication History

Received: 31 May 2024

Accepted after revision: 19 June 2024

Accepted Manuscript online:
19 June 2024

Article published online:
09 July 2024

© 2024. Thieme. All rights reserved

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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 (νasym(O=S=O)N–bound), 1230 (νsym(CF3)), 1195 (νasym(CF3)), 1173 (νsym(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.