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Tetrabutylphosphonium 4-Ethoxyvalerate As a Biomass

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Tetrabutylphosphonium 4-Ethoxyvalerate As a Biomass Chemical Papers (2020) 74:4593–4598 https://doi.org/10.1007/s11696-020-01287-y ORIGINAL PAPER Tetrabutylphosphonium 4‑ethoxyvalerate as a biomass‑originated media for homogeneous palladium‑catalyzed Hiyama coupling reactions László Orha1,2 · Ábrahám Papp1 · József M. Tukacs1 · László Kollár3 · László T. Mika1 Received: 23 May 2020 / Accepted: 13 July 2020 / Published online: 23 July 2020 © The Author(s) 2020 Abstract The introduction of a biomass-derived ionic liquid into the Hiyama coupling reactions, which has been considered as a powerful tool for the synthesis of symmetrically and non-symmetrically substituted biaryl structures, could further control or even reduce the environmental impact of this transformation. It was shown that tetrabutylphosphonium 4-ethoxyvaler- ate, a γ-valerolactone-based ionic liquid, can be utilized as an alternative solvent to create carbon–carbon bonds between aryl iodides and functionalized organosilanes in the presence of 1 mol% Pd under typical Hiyama conditions (130 °C, 24 h, tetrabutylammonium fuoride activator). A comparison of diferent ionic liquids was performed, and the efects of the cata- lyst precursor and the moisture content of the reaction mixture on the activity of the catalyst system were investigated. The functional group tolerance was also studied, resulting in 15 cross-coupling products (3a–o) with isolated yields of 45–72% and excellent purity (> 98%). Keywords Hiyama coupling · Ionic liquids · Homogeneous catalysis · Green chemistry Introduction received outstanding interest, due to their excellent chemo- selectivity, functional group tolerance, and mild operation The transition-metal-catalyzed cross-coupling reactions have conditions, which are of great importance in the synthesis emerged as one of the most powerful tools for the creative of pharmaceuticals and agrochemicals (Devendar et al. construction of both C–C and C–X (X: heteroatom) bonds, 2018; Johansson Seechurn et al. 2012; Biajoli et al. 2014; especially in multistep synthesis of biologically active com- González-Sebastián and Morales–Morales 2019). Among pounds (Yang et al. 2017; Shi et al. 2011; Hosseinian et al. these reactions, the Hiyama coupling represents an excel- 2018; Jana et al. 2011). From the series of typically applied lent protocol for the synthesis of symmetrically and non- d10 metals, the palladium-catalyzed transformations have symmetrically substituted biaryl structures via coupling of corresponding aryl halides and organosilanes (Hatanaka and Electronic supplementary material The online version of this Hiyama 1988; Sore et al. 2012; Nakao and Hiyama 2011). article (https ://doi.org/10.1007/s1169 6-020-01287 -y) contains The latter, as transmetalation reagents exhibit several advan- supplementary material, which is available to authorized users. tages over organoboranes or organostannanes, such as low cost, low toxicity, ready availability, and high chemical sta- * László T. Mika [email protected] bility. The protocol exhibits high regio- and stereochemistry, as well (Horn 1995; Nakao and Hiyama 2011). The silicon 1 Department of Chemical and Environmental Process waste of the reaction can easily be incinerated to harmless Engineering, Budapest University of Technology SiO . All of these points have made the Hiyama coupling an and Economics, Műegyetem rkp. 3, Budapest 1111, Hungary 2 2 environmentally attractive method; however, it had received Institute of Isotopes, Konkoly-Thege Miklós str. 29-33, limited attention in comparison with Heck, Sonogashira, or Budapest 1121, Hungary Suzuki reaction, before the improved synthetic approaches 3 Department of Inorganic Chemistry, University of Pécs towards novel organosilane compounds renewed its impor- and János Szentágothai Research Center and MTA-PTE Research Group for Selective Chemical Synthesis, Ifúság tance (Denmark and Regens 2008; Denmark and Liu 2010). u. 6, Pécs 7624, Hungary Depending on the structure and/or nature of organosilanes, Vol.:(0123456789)1 3 4594 Chemical Papers (2020) 74:4593–4598 i.e., vinyl silanes (Wolf and Lerebours 2004), alkoxysilanes, Experimental silanols (Hirabayashi et al. 1999), and silanolates (Denmark et al. 2008), a huge variety of application scope can be drawn Materials and equipment including representation of a key step in the total synthesis of complex structures, for example, the total synthesis of The sources of chemicals are listed in the Supplementary (+)–brasilenyne (Denmark and Yang 2004) and of (+)-papu- Material. The γ-valerolactone-based ionic liquids were lacandin D (Denmark et al. 2007). prepared by a published method with details presented in Despite these advantages, the Hiyama couplings are usu- Supplementary Material. ally performed in common organic solvents, which usually The NMR spectra were recorded on a Brucker Avance have high toxicity, fammability, and vapor pressure even at 250 MHz spectrometer. Water contents of the ionic liquids low temperatures resulting in serious environmental con- were determined by Karl Fischer titration performed by cerns. As reported by U.S. FDA guidelines (CDER 2017), HANNA Instruments 904. GC analyses were performed the commonly used solvents for the Hiyama reactions such on an Agilent 6890 N instrument with HP-Innowax capil- as tetrahydrofuran (Miller and Montgomery 2014; Cheng lary column (15 m × 0.25 μm × 0.25 μm) using H2 as a et al. 2013), dioxane (Zhang et al. 2014), N,N-dimethylfor- carrier gas. mamide (Handy et al. 2005), toluene (Denmark et al. 2008), and 1,2-dichloroethane (Ramgren and Garg 2014) are classi- fed into Class 1 and 2, which utilizations should be avoided General procedure for Hiyama coupling reactions or limited, respectively, particularly in the pharmaceutical industry. To eliminate these hazardous auxiliary materials, In a 4 mL screw-cap vial, 0.5 mmol of the corresponding the reactions have been demonstrated in alternative media, iodoarene compounds, 1.5 eq of the corresponding silane, e.g., water (Sakon et al. 2017; Inés et al. 2011; Wolf and 1.5 eq of tetrabutylammonium fuoride (TBAF), 0.01 eq Lerebours 2004) or glycerol (Marset et al. 2018). Although, PdCl2(PPh3)2, and 0.8 mL of tetrabutylphosphonium 4-eth- numerous Pd-catalyzed coupling reactions such as Suzuki, oxyvalerate ([TBP][4EtOV]) ionic liquid were mixed and Sonogashira, Heck, and Stille were demonstrated in ionic stirred at 130 °C for 24 h. After cooling, the mixture was liquids (ILs) (Li et al. 2018; Prechtl et al. 2010; Hallett and partitioned between 5 mL of 1 M HCl and 5 mL of pen- Welton 2011), which have been utilized as versatile and eas- tane. The aqueous phase was extracted subsequently with ily tunable alternative reaction media, and only a few studies 3 × 5 mL of pentane. The combined organic phase was were published on the Hiyama reaction (Mandal et al. 2019). washed with brine, dried over MgSO 4, and fltered, and First, Slattery and co-workers demonstrated the applicabil- the solvent was evaporated under reduced pressure (ca. ity of 1-pentyl-1-methylpyrrolidinium bis(trifuoromethyl- 1.333 kPa). The residue was purifed by chromatography sulfonyl)imide ([C5MPyrr][Tf2N]) as a reaction media for on silica gel (Merck Silicagel 60 (0.063−0.200 mm) for allyl–aryl coupling under mild conditions (Bäuerlein et al. column chromatography (70−230 mesh ASTM)) eluted 2009). Jain developed a phosphane-free protocol for the with n-pentane:EtOAc. The detailed experimental proce- manufacture of functionalized biaryls with good to excellent dure, as well as the characterization of isolated compounds yields in 3-(3-cyanopropyl)-1-methyl-1H-imidazol-3-ium are provided in the Supporting Information. hexafuorophosphate ([CN-bmim][PF6]) by the use of in situ generated Pd nanoparticles (Premi and Jain 2013). The efect of the ILs on the stabilization of Pd nanoparticles was also Preparation and characterization of isolated shown. However, acceptable isolated yields were achieved in compounds the presence of a common co-solvent (Planellas et al. 2014). Although Hiyama coupling is a well-known transforma- Preparation and characterization of earlier published com- tion, according to the best of our knowledge, it has not been pounds (3a–k and 3 m–o) are presented in Supporting carried out in biomass-originated ILs, which could addi- Information. tionally act as a ligand. Therefore, by the introduction of 1-Phenyl-2-chloro-4-(trifuoromethyl)benzene (3 l) was a biomass-based solvent into this synthetically important prepared according to general procedure using 0.5 mmol reaction, the environmental impacts of a Hiyama reaction 2-chloro-1-iodo-4-(trifuoromethyl)benzene, 0.75 mmol involved synthesis could be further controlled and reduced. triethoxyphenylsilane, 0.75 mmol [N(C4H9)4][F]. Iso- 1 Herein, we report a study on the palladium-catalyzed lated yield: 50%. H NMR (250 MHz, CDCl 3): δ (ppm) Hiyama coupling reactions to synthesize various biaryl 7.42–7.51 (m, 5H), 7.51–7.54 (m, 1H), 7.56–7.65 (m, 1H), 13 structures in biomass-originated γ-valerolactone-based 7.76–7.83 (m, 1H). C NMR (62.9 MHz, CDCl 3) 123.8 ionic liquid tetrabutylphosphonium 4-ethoxyvalerate ([TBP] (q, J = 272 Hz), 124.1 (q, J = 3.8 Hz), 127.4 (q, J = 3.8 Hz), [4EtOV]) extending its utilization for catalysis. 1 3 Chemical Papers (2020) 74:4593–4598 4595 128.7, 128.8, 129.6, 131.3 (q, J = 33.4 Hz), 132.2, 133.6, Table 1 Palladium-catalyzed Hiyama coupling reactions of iodoben- 138.5. HRMS [M + H]+ Calculated: 257.0345, Measured: zene (1a) and triethoxyphenylsilane (2a) 257.0341 (0.5 ppm). Entry Ionic liquids Isolated yield (%) Results and discussion 1 [BMIM][PF6] < 5 2 [BMIM][BF4] < 1 The applications of ionic liquids into the synthesis protocols 3 [BMIM][OctS] < 1 have become into the focus of interest due to their versatil- 4 [TEA][4HV] 10 ity and tunability. However, it was shown that the number 5 [TBA][4HV] 8 of chemical steps could be over 20 or even 30, reducing 6 [TBP][4EtOV] 58 their impact towards green chemistry (Jessop 2011). Using a biomass-originated building block for the synthesis of an Reaction conditions: solvent 0.5 mL, 0.5 mmol iodobenzene, 0.75 mmol triethoxyphenylsilane, 1 mol% Pd(OAc)2, 1.5 eq TBAF, T = IL, this number could be signifcantly reduced.
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