Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins

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Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins ( ru-catalyzed-repetitive-batch-borylative-coupling-olefins )

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catalysts Article Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems Jakub Szyling 1,2,* , Tomasz Sokolnicki 1,2, Adrian Franczyk 1 and Je ̨drzej Walkowiak 1,* 1 CenterforAdvancedTechnology,AdamMickiewiczUniversityinPoznan ́,UniwersytetuPoznan ́skiego10, 61-614Poznan ́,Poland;tomasz.sokolnicki@amu.edu.pl(T.S.);adrian.franczyk@amu.edu.pl(A.F.) Faculty of Chemistry, Adam Mickiewicz University in Poznan ́, Uniwersytetu Poznan ́skiego 8, 61-614Poznan ́,Poland 2 * Correspondence: j.szyling@amu.edu.pl (J.S.); jedrzej.walkowiak@amu.edu.pl (J.W.) Received: 8 June 2020; Accepted: 5 July 2020; Published: 8 July 2020 􏰁􏰂􏰃 􏰅􏰆􏰇 􏰈􏰉􏰊􏰋􏰌􏰂􏰍 Abstract: The first, recyclable protocol for the selective synthesis of (E)-alkenyl boronates via borylative coupling of olefins with vinylboronic acid pinacol ester in monophasic (cat@IL) or biphasic (cat@IL/scCO2) systems is reported in this article. The efficient immobilization of [Ru(CO)Cl(H)(PCy3)2] (1 mol%) in [EMPyr][NTf2] and [BMIm][OTf] with the subsequent extraction of products with n-heptane permitted multiple reuses of the catalyst without a significant decrease in its activity and stability (up to 7 runs). Utilization of scCO2 as an extractant enabled a significant reduction in the amount of catalyst leaching during the separation process, compared to extraction with n-heptane. Such efficient catalyst immobilization allowed an intensification of the processes in terms of its productivity, which was indicated by high cumulative TON values (up to 956) in contrast to the traditional approach of applying volatile organic solvents (TON = ~50–100). The reaction was versatile to styrenes with electron-donating and withdrawing substituents and vinylcyclohexane, generating unsaturated organoboron compounds, of which synthetic utility was shown by the direct transformation of extracted products in iododeborylation and Suzuki coupling processes. All synthesized compounds were characterized using 1H, 13C NMR and GC-MS, while leaching of the catalyst was detected with ICP-MS. Keywords: homogeneous catalysis; ionic liquids; supercritical CO2; borylative coupling; catalyst recycling; green chemistry; ruthenium catalyst; vinyl boronates; organoboron compounds 1. Introduction Homogeneous catalysis has remained a key part of chemistry for several decades and is a powerful tool in the synthesis of valuable compounds. The high activity and selectivity of molecular catalysts under mild reaction conditions, the lack of diffusion barriers in comparison to heterogeneous systems, and the variability of their electronic and steric properties tuned by the proper design and choice of ligands and metal centers lead to their application in the chemical industry in the production of advanced polymers and fine chemicals [1,2]. On the other hand, homogeneous conditions generate notable problems in recovery and reuse of catalysts, which are mostly based on expensive noble transition metals (TM), for example, rhodium, iridium, platinum, palladium, or ruthenium. To obtain high TON values and the proper process selectivity, this precious catalyst is often sacrificed within the separation process. Moreover, homogeneous conditions require a considerable amount of volatile organic solvent to dissolve all reaction components: reagents and catalysts. Such an approach generates problems with the process economy resulting from the high solvent consumption within the process Catalysts 2020, 10, 762; doi:10.3390/catal10070762 www.mdpi.com/journal/catalysts

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