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Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine–Palladium Complex Under Aerobic Conditions

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Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine–Palladium Complex Under Aerobic Conditions Trans. Mat. Res. Soc. Japan 40[2] 103-106 (2015) Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine–Palladium Complex under Aerobic Conditions Toshimasa Suzuka,* Mika Adachi, and Kazuhito Ogihara Department of Chemistry, Biology and Marine Science, University of the Ryukyus, Nishihara Okinawa 903-0213, Japan Fax: 81-098-895-8531, e-mail: [email protected] The palladium-catalyzed coupling reaction between an aryl halide and a terminal alkyne, the so-called Sonogashira coupling reaction, was found to occur in water under copper-free conditions using an amphiphilic polystyrene–poly(ethylene glycol) (PS-PEG) resin-supported palladium–terpyridine complex, giving the corresponding aryl-substituted alkyne in high yield. The PS-PEG resin-supported palladium–terpyridine catalyst was recovered simply by filtering the product mixture under air and could be reused three times with only slightly decreased catalytic activity after each use. Key words: Sonogashira, palladium, terpyridine, water, cross-coupling 1. INTRODUCTION organic solvent or metal-contaminated wastes are The palladium-catalyzed coupling reaction produced; and (2) the presence of oxygen and between an aryl halide and a terminal alkyne, the moisture do not negatively affect the reaction. so-called Sonogashira reaction [1], is recognized These benefits therefore allow the Sonogashira as being the most successful method for forming coupling reaction to be performed meeting the an sp2 carbon–sp3 carbon bond. Since its requirements of “green chemistry”. discovery by Sonogashira and co-workers in 1975, a vast amount of research has been performed cat 1. ( 5mol% Pd) into its synthetic applications and on improving X + R1 R1 the reaction efficiency [2]. However, one of the Et3N, in H2O 100 °C, 12 h, air 2 3 4 major problems with using the Sonogashira (without Cu) reaction lies in the reaction conditions that are required. The use of a homogeneous mixture of a palladium catalyst and a copper reagent PEG 3000 N O (co-catalyst) is frequently required to promote the PS O N C N Pd+Cl n H reaction, and this leads to the coupling products Cl- n = 60~74 N being contaminated with considerable amounts of 1 metal residues. We have recently developed a copper-free Sonogashira coupling reaction using Scheme 1. Sonogashira reaction in water using a polymer-supported palladium catalyst in water the PS-PEG–terpyridine–Pd complex 1 under an inert gas atmosphere [3]. The polymeric catalyst consists of a polymer, a linkage moiety, 2. EXPERIMENTAL SECTION and a catalytic center prepared from a transition 2.1 General methods metal and a phosphine-based ligand. Therefore, All of the procedures were carried out under the catalytic reactions are carried out under aerobic conditions. Water was deionized using a nitrogen atmosphere to avoid the phosphine Millipore Milli-Q Gradient A10 system. NMR ligands being oxidized [4,5]. spectra were recorded using a Bruker AVANCE 1 We recently developed an amphiphilic spectrometer (500 MHz for H and 125 MHz for 13 polystyrene–poly(ethylene glycol) (PS-PEG) C), a Bruker AV400N spectrometer (400 MHz 1 13 resin-supported terpyridine–metal complex. We for H and 100 MHz for C), and a Hitachi 1 have found that it is an effective catalyst for R1900 spectrometer (90 MHz for H and 22 MHz 13 1 13 coupling reactions in water under heterogeneous for C). H and C NMR spectra were recorded and aerobic conditions, and that it is highly at 25 °C, with the compound for analysis recyclable when used in that way [6]. As an dissolved in CDCl3 or dimethyl sulfoxide-d6 13 extension to that study, we investigated the (DMSO-d6). The C chemical shifts are given ability of a PS-PEG-supported relative to the CDCl3 and DMSO-d6 internal terpyridine–palladium(II) complex standards (δ 77.0 ppm and 39.7 ppm, (PS-PEG–terpyridine–Pd) to catalyze the respectively). Mass spectra were measured using Sonogashira coupling reaction in water. Herein, a JEOL JMS-T100GCv MS (gas we report the results of this investigation, and chromatography–mass spectrometry) instrument show that the complex effectively catalyzes the or a JEOL JMS-T100LP MS (liquid Sonogashira coupling reactions between various chromatography–mass spectrometry) instrument, aryl halides and alkynes in water under aerobic and the base peak of a mass spectrum is labeled conditions (Scheme 1). This catalyst system “bp.” Gas chromatography and infra-red offers two benefits over other systems: (1) no spectroscopy analyses were performed using a 103 104 Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine-Palladium Complex under Aerobic Conditions Shimadzu GC-2014 instrument and a Jasco 33.1 Hz, 1 C), 128.8, 128.4, 126.4 (q, J = 272 Hz, 129.5, 128.5, 128.4, 128.3, 124.9, 122.7, 90.5, iodobenzene derivatives 2e, 2f, and 2g (which FTIR-410 instrument, respectively. Inductively 1 C), 125.2 (q, J = 272 Hz, 1 C), 122.5, 91.7, 87.8. MS (EI): m/z (rel %) 212 (bp, M+), 176 (46), each have methyl substituents at the meta- or coupled plasma–atomic emission (ICP–AES) 87.9. MS (EI): m/z (rel %) 246 (73, M+), 176 (43), 151 (13). IR (ATR): v (cm−1) 3055, 1490. CAS ortho-positions) gave −1 spectra were acquired using a Shimadzu 98 (bp), 75 (49), 51 (46). IR (ATR): v (cm ) registry number: 51624-34-1. 1-phenyl-2-(o-tolyl)acetylene (4e) in 57% yield, ICPE-9000 instrument. 3080, 2219, 1508. CAS registry number: 1-phenyl-2-(m-tolyl)acetylene (4f) in 71% yield, 370-99-0. 3. RESULTS AND DISCUSSION and 1-(1-naphthyl)-2-phenylacetylene (4g) in 2.2 Materials We developed a Sonogashira coupling reaction 79% yield, respectively (runs 5–7). The PS-PEG–terpyridine–Pd (1) was prepared 1-(p-Methoxycarbonylphenyl)-2-phenylacetylene for aryl iodides and bromides using the polymeric Bromobenzene 2j was reacted with 3 using a 1 from a PS-PEG-NH2 resin (Tenta Gel S NH2, with (4d): H NMR (CDCl3) δ 8.02 (d, J = 8.5 Hz, 2 H), catalyst 1 in water. The polymeric catalyst was longer reaction time (24 h) than was used for the an average diameter of 90 µm, 1% divinylbenzene 7.59 (d, J = 8.5 Hz, 2 H), 7.57–7.53 (m, 2 H), readily prepared from other reactions, and this reaction gave the cross-links, and an amino residue loading value 7.38–7.36 (m, 3 H), 3.93 (s, 3 H). 13C NMR 4-methoxycarbonylbenzaldehyde, corresponding acetylene derivative 4a in 1.6% of 0.31 mmol/g, purchased from Rapp Polymer), a (CDCl3) δ 166.5, 131.7, 131.4, 129.5, 129.4, 2-acetylpyridine, NH4OH, PS-PEG-NH2 resin, yield (run 11). polymeric terpyridine ligand, and 128.7, 128.4, 127.9, 122.6, 92.4, 88.6, 52.9. MS and (C6H5CN)2PdCl2 following the procedures + (C6H5CN)2PdCl2 following a procedure that has (EI): m/z (rel %) 236 (80, M ), 205 (bp), 176 (91), described elsewhere [6,7]. Table I. Effects of different bases on the been reported previously [6]. The Pd loading 151 (34). IR (ATR): v (cm−1) 2949, 2217, 1718, The polymeric catalyst 1 exhibited a high Sonogashira coupling reaction between level in the polymeric catalyst 1 was 0.26 1606, 1508, 1455, 1374, 1280. CAS registry catalytic activity for the Sonogashira coupling iodobenzene and phenylacetylene using polymeric mmol/g. number: 42497-80-3. reaction. Iodobenzene (2a) and phenylacetylene 3 catalyst 1 in watera PS-PEG-terpyridine-Pd 1 were coupled in water using catalyst 1 (5 mol% 5 mol% I + 2.3 Sonogashira coupling reaction 1 Pd) in the presence of 3 equiv. of base at 100 °C base, 100 °C, 12 h The procedure used to obtain the Sonogashira 1-Phenyl-2-(o-tolyl)acetylene (4e): H NMR for 12 h. The reaction mixture was filtered and air, in H2O coupling reaction product 4a is described here. (CDCl3) δ 7.44-7.39 (m, 3 H), 7.25–7.21 (m, 3 H), the recovered resin beads were rinsed with a 2a 3 4a The Sonogashira coupling reaction products 4b–i 7.12–7.10 (m, 2 H), 7.08–7.04 (m, 1 H), 2.41 (s, 3 small portion of water and then extracted with 13 Run Base Yield were obtained using this procedure with slight H). C NMR (CDCl3) δ 166.5, 131.7, 131.4, EtOAc to give diphenylacetylene (4a). modifications. Iodobenzene (2a; 81.6 mg, 0.40 129.5, 129.4, 128.7, 128.4, 127.9, 122.6, 92.4, We used different bases in the Sonogashira + 1 32 88.6, 52.9. MS (EI): m/z (rel %) 192 (bp, M ), Li2CO3 mmol) was added to a mixture of the polymeric −1 coupling reaction using catalyst 1 in water to catalyst 1 (80 mg, 0.020 mmol), the base Et N 165 (27), 115 (11).IR (ATR): v (cm ) 3055, 2919, identify which bases were most suitable for use in 3 2 Na CO 28 (121 mg, 1.2 mmol), and phenylacetylene (3; 81.7 1600, 1492. CAS registry number: 14309-60-5. the reaction (Table I). The reaction efficiencies 2 3 mg, 0.80 mmol) in H2O (3.0 mL). The reaction were very different for different bases. Lithium 3 K CO 45 mixture was shaken at 100 °C for 12 h and then carbonate, sodium carbonate, potassium carbonate, 2 3 1-Phenyl-2-(m-tolyl)acetylene (4f): 1H NMR filtered. The resin beads that were recovered were and cesium carbonate gave 4a in 32%, 28%, 45%, (CDCl ) δ 7.51 ( d, J = 5.8 Hz, 2 H), 7.35–7.28 4 47 rinsed with H O and extracted three times with 3 and 47% yields, respectively (runs 1–4).
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