New Polymeric Disulfonimide for Heterogeneous Silicon Lewis Acid Catalysis

Giuliana Giorgianni; Maria Edith Casacchia; Pier Carlo Ricci; Simone Di Muzio; Andrea Lazzarini; Armando Carlone; Fabio Pesciaioli

doi:10.1055/a-2349-1863

Synlett, Inhaltsverzeichnis

Synlett 2025; 36(04): 426-430
DOI: 10.1055/a-2349-1863

letter

New Polymeric Disulfonimide for Heterogeneous Silicon Lewis Acid Catalysis

Giuliana Giorgianni‡

^aDipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy

,

Maria Edith Casacchia‡

^aDipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy

^bIUSS Scuola Universitaria Superiore di Pavia, Palazzo del Broletto, Piazza della Vittoria, 15 27100, Pavia, Italy

,

Pier Carlo Ricci

^cDipartimento di Fisica, Università di Cagliari, sp 8, km 0.700, 09042 Monserrato, Italy

,

Simone Di Muzio

^aDipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy

^dIstituto dei Sistemi Complessi, ISC-CNR U.O.S. Sapienza, P.le A. Moro 5, 00185 Rome, Italy

,

Andrea Lazzarini

^aDipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy

,

Armando Carlone

^aDipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy

,

Fabio Pesciaioli ∗

^aDipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio, 67100 L’Aquila, Italy

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Abstract

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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

Volltext

Referenzen

References and Notes

1a Sheldon RA, Arends I, Hanefelds U. Green Chemistry and Catalysis 2007
1b Ahluwalia VK, Kidwai M. Basic Principles of Green Chemistry: New Trends in Green Chemistry 2004
1c Anastas PT, Warner JC. Green Chemistry: Theory and Practice 1998

2a Acid Catalysis in Modern Organic Synthesis . Yamamoto H, Ishihara K. Wiley-VCH; Weinheim: 2009
2b Walker JC. L, Klare HF. T, Oestreich M. Nat. Rev. Chem. 2020; 4: 54
2c Konwar LJ, Mäki-Arvela P, Mikkola J.-P. Chem. Rev. 2019; 119: 11576
2d Gupta P, Paul S. Catal. Today 2014; 236: 153
2e Olah GA, Iyer PS, Surya Prakash GK. Synthesis 1986; 513
2f Yamamoto H. Top. Organomet. Chem. 2013; 44: 315

For selected examples in achiral DSI-based Brønsted acid catalysis, see:

3a Subba Reddy BV, Ghanty S. Synth. Commun. 2014; 44: 2545
3b Jin Y, Ji Y, He X, Kan S, Xia H, Liang B, Chen J, Wu H, Guo K, Li Z. Polym. Chem. 2014; 5: 3098
3c Barbero M, Cadamuro S, Dughera S, Venturello P. Synthesis 2008; 1379
3d Barbero M, Cadamuro S, Dughera S, Venturello P. Synthesis 2008; 3625

For selected examples in enantioselective DSI-based Brønsted acid catalysis, see:

4a Wakchaure VN, List B. Angew. Chem. Int. Ed. 2016; 55: 15775
4b Prévost S, Dupré N, Leutzsch M, Wang Q, Wakchaure V, List B. Angew. Chem. Int. Ed. 2014; 53: 8770
4c Wakchaure VN, Kaib PS. J, Leutzsch M, List B. Angew. Chem. Int. Ed. 2015; 54: 11852

5a Sharif I, Creager S, DesMarteau DD. Handbook of Fluoropolymer Science and Technology 2014; 521
5b Sutradhar SC, Yoon S, Ryu T, Jin L, Zhang W, Kim W, Jang H. Membranes 2021; 11: 49
5c Zhang Y, Ting JW. Y, Rohan R, Cai W, Li J, Xu G, Chen Z, Lin A, Cheng H. J. Mater. Sci. 2014; 49: 3442
5d Flach AM, Johnson FE, Cabasso I. Polym. Chem. 2013; 4: 3370
5e Bekiarian PG, Doyle M, Farnham WB, Feiring AE, Morken PA, Roelofs MG, Marshall WJ. J. Fluorine Chem. 2004; 125: 1187
5f Thomas BH, Shafer G, Ma JJ, Tu M.-H, DesMarteau DD. J. Fluorine Chem. 2004; 125: 1231
5g Rahman MdK, Aiba G, Susan MdA. B. H, Watanabe M. Electrochim. Acta 2004; 50: 633
5h Sutradhar SC, Yoon S, Ryu T, Jin L, Zhang W, Kim W, Jang H. Membranes 2021; 11: 168
5i Li G.-F, Yang D, Abel ChuangP.-Y. ACS Catal. 2018; 8: 11688

For selected examples and reviews on achiral DSI-based silicon Lewis acid catalysis, see:

6a Zhao W, Sun J. Chem. Rev. 2018; 118: 10349
6b Bae HY, List B. Chem. Eur. J. 2018; 24: 13767
6c Barbero M, Bazzi S, Cadamuro S, Dughera S, Magistris C, Smarra A, Venturello P. Org. Biomol. Chem. 2011; 9: 2192
6d Boxer MB, Yamamoto H. J. Am. Chem. Soc. 2006; 128: 48

For selected examples and reviews on enantioselective DSI-based silicon Lewis acid catalysis, see:

7a James T, van Gemmeren M, List B. Chem. Rev. 2015; 115: 9388
7b Zhang Z, Bae HY, Guin J, Rabalakos C, van Gemmeren M, Leutzsch M, Klussmann M, List B. Nat. Commun. 2016; 7: 12478
7c Tap A, Blond A, Wakchaure VN, List B. Angew. Chem. Int. Ed. 2016; 55: 8962
7d Guin J, Wang Q, van Gemmeren M, List B. Angew. Chem. Int. Ed. 2015; 54: 355
7e Ratjen L, van Gemmeren M, Pesciaioli F, List B. Angew. Chem. Int. Ed. 2014; 53: 8765
7f Wang Q, van Gemmeren M, List B. Angew. Chem. Int. Ed. 2014; 53: 13592
7g Gandhi S, List B. Angew. Chem. Int. Ed. 2013; 52: 2573
7h Wang Q, Leutzsch M, van Gemmeren M, List B. J. Am. Chem. Soc. 2013; 135: 15334
7i Mahlau M, García-García P, List B. Chem. Eur. J. 2012; 18: 16283
7j Ratjen L, García-García P, Lay F, Beck ME, List B. Angew. Chem. Int. Ed. 2011; 50: 754
7k García-García P, Lay F, García-García P, Rabalakos C, List B. Angew. Chem. Int. Ed. 2009; 48: 4363

8a Pal R, Sarkar T, Khasnobis S. ARKIVOC 2012; 570

9 Harmer MA, Sun Q. Appl. Catal., A 2001; 221: 45
10 Antenucci A, Marra F, Dughera S. RSC Adv. 2021; 11: 26083

For selected examples on metal-based silicon Lewis acid catalysis, see:

11a Miyamura H, Sonoyama A, Hayrapetyan D, Kobayashi S. Angew. Chem. Int. Ed. 2015; 54: 10559
11b Shintaku H, Nakajima K, Kitano M, Hara M. Chem. Commun. 2014; 50: 13473
11c Olmos A, Alix A, Sommer J, Pale P. Chem. Eur. J. 2009; 15: 11229
11d Doherty S, Goodrich P, Hardacre C, Pârvulescu V, Paun C. Adv. Synth. Catal. 2008; 350: 295
11e Iwanami K, Sakakura T, Yasuda H. Catal. Commun. 2009; 10: 1990

12 Moumene T, Belarbi EH, Haddad B, Villemin D, Abbas O, Khelifa B, Bresson S. J. Mol. Struct. 2015; 1083: 179
13 For further details see the Supporting Information.
14 Zhang Y, Lay F, García-García P, List B, Chen EY.-X. Chem. Eur. J. 2010; 16: 10462
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.

Zusatzmaterial

Supporting Information