Anion Metathesis in Facile Preparation of Olefin Metathesis Catalysts Bearing a Quaternary Ammonium Chloride TagThe authors are grateful to the ‘Catalysis for the Twenty-First Century Chemical Industry’ project carried out within the TEAM-TECH programme of the Foundation for Polish Science co-financed by the European Union from the European Regional Development under the Operational Programme Smart Growth. The study was carried out at the Biological and Chemical Research Centre, University of Warsaw, established within the project co-financed by European Union from the European Regional Development Fund under the Operational Programme Innovative Economy, 2007–2013.
Received: 18 February 2019
Accepted after revision: 25 April 2019
20 May 2019 (eFirst)
◊ J.P. and M.P. contributed equally to this work
Dedicated to Professor Mieczysław Mąkosza on the occasion of his 85th birthdayó
Published as part of the Cluster Metathesis beyond Olefins
Easy and efficient method for preparation of all-chloro ruthenium catalysts bearing a quaternary ammonium tag was developed. The key anion metathesis reaction was made with AgCl, and the facile recycling of silver wastes was demonstrated. The developed method transforms more accessible, yet poorly characterised mixed chloro/iodo Ru complexes into valuable all-chloro catalysts, useful in aqueous metathesis. Practical utility of the developed anion metathesis reaction was demonstrated by preparation of a commercial Ru catalyst, StickyCat™, on a 5 gram scale.
References and Notes
- 1a Olefin Metathesis: Theory and Practice . Grela K. John Wiley & Sons; Hoboken, NJ: 2014
- 1b Handbook of Metathesis . Grubbs RH, Wenzel AG, O’Leary DJ, Khosravi E. Wiley-VCH; Weinheim: 2014
- 1c Michrowska A, Grela K. Pure Appl. Chem. 2008; 80: 31
- 2 Higman CS, Lummiss JA. M, Fogg DE. Angew. Chem. Int. Ed. 2016; 55: 3552
- 3a Lin YA, Davis BG. Beilstein J. Org. Chem. 2010; 6: 1219
- 3b Tomasek J, Schatz J. Green Chem. 2013; 15: 2317
- 3c Sabatino V, Ward TR. Beilstein J. Org. Chem. 2019; 15: 445
- 3d McKay CS, Finn MG. Chem. Biol. 2014; 21: 1075
- 4a Śledź P, Mauduit M, Grela K. Chem. Soc. Rev. 2008; 37: 2433
- 4b Queval P, Rouen M, Gaumont AC, Dez I, Baslé O, Mauduit M. In Olefin Metathesis: Theory and Practice . Grela K. John Wiley & Sons; Hoboken: 2014: 547
- 4c Fischmeister C. In Catalytic Alkene Metathesis in Ionic Liquids, NATO Science Series II: Mathematics, Physics and Chemistry, Metathesis Chemistry. Springer; Dordrecht: 2007: 483
- 5a Burtscher D, Grela K. Angew. Chem. Int. Ed. 2009; 48: 442
- 5b Lipshutz BH, Ghorai S. In Olefin Metathesis: Theory and Practice . Grela K. John Wiley & Sons; Hoboken: 2014: 515
- 5c Wang ZJ, Jackson WR, Robinson AJ. Green Chem. 2015; 17: 3407
- 6 Masuda S, Tsuda S, Yoshiya T. Org. Biomol. Chem. 2018; 16: 9364
- 7 Wright DB, Touve MA, Thompson MP, Gianneschi NC. ACS Macro Lett. 2018; 7: 401
- 8a Chołuj A, Zieliński A, Grela K, Chmielewski MJ. ACS Catal. 2016; 6: 6343
- 8b Pastva J, Skowerski K, Czarnocki SJ, Žilková N, Čejka J, Bastl Z, Balcar H. ACS Catal. 2014; 4: 3227
- 8c Öztürk B. Ö, Gürcü D, Şehitoğlu SK. J. Organomet. Chem. 2019; 883: 11
- 8d Byrnes MJ, Hilton AM, Woodward CP, Jackson WR, Robinson AJ. Green Chem. 2012; 14: 81
- 8e Skowerski K, Białecki J, Czarnocki SJ, Żukowska K, Grela K. Beilstein J. Org. Chem. 2016; 12: 5
- 8f Michrowska A, Mennecke K, Kunz U, Kirschning A, Grela K. J. Am. Chem. Soc. 2006; 128: 13261
- 9 Skowerski K, Pastva J, Czarnocki SJ, Janoscova J. Org. Process Res. Dev. 2015; 19: 872
- 10 Grimm AR, Sauer DF, Davari MD, Zhu L, Bocola M, Kato S, Onoda A, Hayashi T, Okuda J, Schwaneberg U. ACS Catal. 2018; 8: 3358
- 11a Gułajski Ł, Mauduit M, Grela K. Pure Appl. Chem. 2009; 81: 2001
- 11b Szczepaniak G, Kosinski K, Grela K. Green Chem. 2014; 16: 4474
- 11c Jana A, Grela K. Chem. Commun. 2018; 54: 122
- 11d Szczepaniak G, Urbaniak K, Wierzbicka C, Kosiński K, Skowerski K, Grela K. ChemSusChem 2015; 8: 4139
- 11e Szczepaniak G, Ruszczyńska A, Kosiński K, Bulska E, Grela K. Green Chem. 2018; 20: 1280
- 11f Szczepaniak G, Nogaś W, Piątkowski J, Rusczyńska A, Bulska E, Grela K. Org. Process Res. Dev. 2019; DOI: DOI: 10.1021/acs.oprd.8b00392.
- 12 Skowerski K, Szczepaniak G, Wierzbicka C, Gułajski Ł, Bieniek M, Grela K. Catal. Sci. Technol. 2012; 2: 2424
- 13 https://www.sigmaaldrich.com/catalog/product/aldrich/295507?lang=pl®ion=PL (accessed Feb 13, 2019).
- 14 Klučiar M, Grela K, Mauduit M. Dalton Trans. 2013; 42: 7354
- 15 Krzysztof Skowerski (Apeiron Synthesis S.A), private communication.
- 16 https://ec.europa.eu/health/documents/eudralex/vol-4_en (accessed Feb 13, 2019).
- 17 For an early example of I– exchange with PF6 – and BF4 –, see: Gułajski Ł, Michrowska A, Narożnik J, Kaczmarska Z, Rupnicki L, Grela K. ChemSusChem 2008; 1: 103
- 18 Gułajski Ł, Grela K. In Green Metathesis Chemistry, NATO Science for Peace and Security Series A: Chemistry and Biology . Dragutan V, Demonceau A, Dragutan I, Finkelshtein ES. Springer Netherlands; Dordrecht: 2010: 49
- 19a Skowerski K, Wierzbicka C, Szczepaniak G, Gułajski Ł, Bieniek M, Grela K. Green Chem. 2012; 14: 3264
- 19b Skowerski K, Gułajski Ł, Bieniek M. PCT Int. Appl WO 2013127880, 2013
- 20 Physical Constants of Organic Compounds. In CRC Handbook of Chemistry and Physics, Internet Version 2005. Lide DR. CRC Press; Boca Raton: 2005
- 21 Salomon M. In Physical Chemistry of Organic Solvent Systems . Covington A. Springer; New York: 1973: 161
- 22 Typical ProcedureA 4 mL oven-dried vial was charged with chloride salt (30 equiv for AgCl, CuCl and NaCl, 15 equiv. for PbCl2 and CuCl2). The vial was evacuated, three times flushed with argon, solution of Ru10 in dry CD2Cl2 (1 mL, concentration 64 mg/mL) was added, and the resulting mixture was stirred for 30 min (600 rpm) at room temperature. The mixture was centrifuged (3 min, 4000 rpm), and the solution was examined by 1H NMR spectroscopy and TLC (alumina plates). Crude product was purified by column chromatography (neutral alumina, 10% DCM/MeOH).
- 23 https://www.apeiron-synthesis.com/katalizatory/fixcat/ (accessed Feb 13, 2019).
- 24 Large-Scale ExperimentIn 100 mL oven-dried round-bottom flask AgCl (0.95 g, 0.66 mmol, 1.1 equiv. per iodide) and Ru10 (containing 91% of [Ru](Cl)2 and 9% of [Ru](Cl)I complexes, NR4 +Cl–: NR4 +I– = 20:80, 5 g, 0.6 mmol, 1 equiv.) were suspended in CH2Cl2 (80 mL), and the resulting mixture was stirred for 30 min (300 rpm) at room temperature. The mixture was centrifuged (4000 rpm), filtered through Büchner funnel with Teflon filter (pore size 0.2 μm) and flushed with MeOH. Filtrate was filtered through short pad of neutral Celite® (5 g), solvent was evaporated, crude product was dissolved in minimal amount of CH2Cl2, and precipitated with heptane. Precipitate was washed with diethyl ether and dried overnight under vacuum to afford Ru4 as a light green powder (4.16 g, 95%).
- 25 Silver RecyclingIn a 50 mL beaker the mixture of silver halides (1 g) was dissolved in H2SO4 (1 mL). H2O2 (50% aqueous solution) was slowly added until evacuation of iodine was finished (approx. 1.2 mL). The mixture was stirred for 1 h at 110 °C, cooled to room temperature, diluted with H2O (20 mL), and treated with concentrated HCl to precipitate crude AgCl. Colourless precipitate was filtered, washed with water, and solubilised in ammonia. Water (20 mL) was added followed by concentrated HCl to precipitate AgCl which was filtered, washed with water, acetone, diethyl ether, and dried overnight under high vacuum at 80 °C to provide pure product with 83% yield ( 858 mg).
- 26 We are grateful to the referee for this suggestion.
For a review on bioorthogonal bioconjugation reactions, see:
For the first example, see: