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Catalysts 2020, 10, 762 13 of 15 4. Conclusions The new, effective and highly regio- and stereoselective catalytic systems based on the immobilization of [Ru(CO)Cl(H)(PCy3)2] in ionic liquids for the borylative coupling of vinylboronic pinacol ester with olefins was presented for the first time within these studies. The best results, characterized by excellent product yields, were obtained when [BMIm][OTf] and [EMPyr][NTf2] were used as solvents and catalyst immobilization media. The system permitted a transformation of various vinyl-substituted olefins (styrene (2a), functionalized styrenes (2b–i) and vinylcyclohexane (2j)) into useful borylsubstituted unsaturated products, which can be used in deborylation or Suzuki coupling reactions. The application of ILs permitted catalyst reuse and the carrying out of repetitive batch borylative coupling in monophasic [Ru(CO)Cl(H)(PCy3)2]@ILs or biphasic [Ru(CO)Cl(H)(PCy3)2]@[BMIm][OTf]/scCO2 systems with product extraction with non-polar n-heptane or scCO2. These new protocols, under optimized reaction ([Ru-H]:1:2 = 0.01:1:1.5, 110 ◦C, 6 h, 1 g IL, inert atmosphere conditions) and extraction (3 × 5 mL of the n-heptane at 60 ◦C or 160–180 bar of CO2 at 40 ◦C, 8 mL/min, 45 min) conditions, allowed of the catalyst to be reused 5–7 times without any significant loss of activity or stability. The application of scCO2 as an extractant in monophasic or biphasic solvent systems significantly reduced catalyst leaching during the separation process (<1 ppm in each batch), compared to the extraction with n-heptane. Moreover, the good solubility of the reagents and products in scCO2 and the high catalyst stability creates future possibilities for carrying out this process under a continuous flow method. In addition, it was found that the application of ILs as reaction media has a positive impact on the reaction rate, shortening the process from 24 h to 6 h. Such an approach based on multiple catalyst use enabled an intensification of the cumulative TON values (up to 956) in comparison to the single batch (~50–100), showing the potential of the system reported within this research, which was developed according to the sustainable development rules. The catalyst reuse, simplification of the separation process, increased process productivity and possibilities to carry out the reaction in repetitive batch borylative coupling of olefins are in agreement with green chemistry paradigms. Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/10/7/762/s1, Procedure description of GC-MS, NMR and ICP-MS analyses, NMR spectra for all isolated products (3a–j, 4, 5). Author Contributions: Conceptualization, J.S. and J.W.; methodology, J.S. and J.W.; investigation, J.S. and T.S.; resources, J.S., T.S., A.F. and J.W.; writing—original draft preparation, J.S.; writing—review and editing, J.W., A.F., T.S. and J.S.; supervision, J.W.; funding acquisition, T.S. All authors have read and agreed to the published version of the manuscript. Funding: The APC was funded by grant No. POWR.03.02.00-00-I026/16 co-financed by the EU through the European Social Fund under the Operational Program Knowledge Education Development. Acknowledgments: This work was supported by The National Centre for Research and Development in Poland, Lider Programme No. LIDER/26/527/L-5/13/NCBR/2014 and The National Science Centre No. UMO-2019/32/C/ST4/00235 and The National Centre for Research and Development in Poland, Lider Programme No. LIDER/6/0017/L-9/17/NCBR/2018 and grant No. POWR.03.02.00-00-I026/16 co-financed by the EU through the European Social Fund under the Operational Program Knowledge Education Development. Conflicts of Interest: The authors declare no conflict of interest. References 1. Bhaduri, S.; Mukesh, D. Chemical industry and homogeneous catalysis. In Homogeneous Catalysis; Bhaduri, S., Mukesh, D., Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2014; pp. 1–21. 2. Joshi, S.S.; Bhatnagar, A.; Ranade, V.V. Chapter 8—Catalysis for fine and specialty chemicals. In Industrial Catalytic Processes for Fine and Specialty Chemicals; Joshi, S.S., Ranade, V.V., Eds.; Elsevier: Amsterdam, The Netherlands, 2016; pp. 317–392. 3. Cole-Hamilton, D.J.; Tooze, R.P. Catalyst Separation, Recovery and Recycling: Chemistry and Process Design; Springer Science & Business Media: Berlin/Heidelberg, Germany, 2006; Volume 30, pp. 1–247. 4. Centi, G.; Perathoner, S. Methods and tools of sustainable industrial chemistry: Catalysis. Sustain. Ind. Chem. 2009, 73–198. [CrossRef]PDF Image | Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins
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