Cu based organic frameworks an catalysts for c c and c n coupling reactions

VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY DANG HUYNH GIAO Cu-BASED ORGANIC FRAMEWORKS AS CATALYSTS FOR C–C AND C–N COUPLING REACTIONS PhD THESIS HO CHI MINH CITY 2015 VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY DANG HUYNH GIAO Cu-BASED ORGANIC FRAMEWORKS AS CATALYSTS FOR C–C AND C–N COUPLING REACTIONS Major: Organic Chemical Technology Major code: 62527505 Independent examiner 1: Prof Dr Dinh Thi Ngo Independent examiner 2: Assoc Prof Dr Nguyen Thi Phuong Phong Examiner 1: Assoc Prof Dr Nguyen Cuu Khoa Examiner 2: Assoc Prof Dr Nguyen Thai Hoang Examiner 3: Assoc Prof Dr Le Thi Hong Nhan ADVISORS: Prof Dr Phan Thanh Son Nam Dr Le Thanh Dung DECLARATION OF ORIGINALITY I hereby declare that this is my own research study The research results and conclusions in this thesis are true, and are not copied from any other resources The literature references have been quoted with clear citation as requested Thesis Author Dang Huynh Giao i THESIS SUMMARY This thesis describes the synthesis, characterization and catalytic applications of four copper-based metal-organic frameworks (Cu-MOFs) including Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC) These Cu-MOFs were used as heterogeneous catalysts for direct CC and CN coupling reactions to synthesize propargylamines and quinoxalines The first chapter of this thesis provides a literature review of Cu-MOFs The review is limited in Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC) An overview of their structures, properties, synthesis, characterization methods and catalytic applications is described In addition, the chapter also reviews CC and CN coupling reactions for the synthesis of propargylamines and quinoxalines The second chapter of this thesis discusses the synthesis and characterization of four Cu-MOFs including Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC) These Cu-MOFs were prepared by solvothermal methods and characterized by X-ray powder diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma mass spectrometry (ICP-MS), hydrogen temperature-programmed reduction (H2-TPR) and nitrogen physisorption measurements The third chapter of this thesis describes the evaluation of Cu-MOFs as heterogeneous catalysts for direct CC and CN coupling reactions These Cu-MOFs were found to be highly catalytically active for direct CC and CN coupling reactions The CuMOF catalysts could be recovered and reused several times without a significant degradation in catalytic activity To the best of our knowledge, these transformations using MOFs catalysts were not previously mentioned in the literature ii ABSTRACT Four highly porous Copper-based organic frameworks (Cu-MOFs) such as Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) and Cu(BDC) were synthesized and characterized by X-ray powder diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma mass spectrometry (ICP-MS), hydrogen temperature-programmed reduction (H2-TPR) and nitrogen physisorption measurements Three Cu-MOFs including Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) were used as heterogeneous catalysts for direct CC coupling reactions to synthesize propargylamines Cu(BDC) was employed as heterogeneous catalyst for CN coupling reaction to synthesize quinoxalines These catalytic systems offered practical approaches with high yields and selectivity Additionally, broad functionality was shown to be compatible The Cu-MOFs catalysts could be recovered and reused several times without significant degradation in catalytic activity To the best of our knowledge, these transformations using Cu-MOFs catalysts were not previously mentioned in the literature iii ACKNOWLEDGMENT I reserve special thanks to my research advisors, Prof Dr Phan Thanh Son Nam and Dr Le Thanh Dung, who have supported me over the course of my research work Their motivation, patience, enthusiasm and immense knowledge have kept me going during the past four years I was so lucky to have such a precious opportunity to work under their guidance I really would like to learn more from such renowned and respected chemists I would aslo like to thank Dr Truong Vu Thanh and Assoc Prof Dr Le Thi Hong Nhan for their insight and questions that have undoubtedly helped me progress to this point I would like to thank Dr Hiroyasu Furukawa for guiding me how to recognize and find the best ways to solve the scientific problems I would be remiss if I did not acknowledge all members of my group (Nguyen Kim Chung, Nguyen Thanh Tung, Nguyen Thai Anh, Le Khac Anh Ky, Nguyen Dang Khoa, Nguyen Van Chi, Nguyen Tran Vu, Le Thi Ngoc Hanh) for the stimulating discussions in Organic Chemistry Division Additionally, I wish to acknowledge four undergraduate students (Dang Truong Thinh, Nguyen Thanh Duy, Nguyen Duy Thanh, Dong Anh Quoc) and graduated student (Vu Thi Hai Yen) for their helps during the time they studied in laboratory I also thank to my colleagues in Chemical Engineering Department at CanTho University for their encouragement Especially, I would like to thank Dr Luong Huynh Vu Thanh about help me download the scientific papers I could not download in Viet Nam My deepest gratitude to my family: my parents, my oldest sister Dang Huynh Thu, my older sister Dang Huynh Nhu, my younger brother Dang Quoc Dung and my youngest sister Dang Huynh Anh The support and love from my family is of inestimable value iv TABLE OF CONTENTS TABLE OF CONTENTS v LIST OF FIGURES vii LIST OF SCHEMES xi LIST OF TABLES xiii LIST OF ABBREVIATION xiv INTRODUCTION CHAPTER LITERATURE REVIEW: Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY), Cu(BDC) AND CC, CN COUPLING REACTIONS 1.1 Introduction to metal-organic frameworks 1.2 Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 1.2.1 Structures and properties of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 1.2.2 Synthesis of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 13 1.2.3 Characterization of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 15 1.2.4 Catalytic activities of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) 21 1.3 CC cross coupling reactions 26 1.4 CN cross coupling reactions 33 1.5 Aims and objectives 36 CHAPTER SYNTHESIS AND CHARACTERIZATION OF Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY), AND Cu(BDC) 38 2.1 Introduction 39 2.2 Experimental 40 2.2.1 Materials and instrumentation 40 2.2.2 Synthesis of Cu3(BTC)2 41 2.2.3 Synthesis of Cu2(BDC)2(DABCO) 42 2.2.4 Synthesis of Cu2(BPDC)2(BPY) 42 v 2.2.5 Synthesis of Cu(BDC) 43 2.3 Results and discussions 43 2.3.1 Synthesis and characterization of Cu3(BTC)2 43 2.3.2 Synthesis and characterization of Cu2(BDC)2(DABCO) 48 2.3.3 Synthesis and characterization of Cu2(BPDC)2(BPY) 53 2.3.4 Synthesis and characterization of Cu(BDC) 58 2.4 Conclusion 63 CHAPTER CATALYTIC STUDIES OF Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY) AND Cu(BDC) ON CC AND CN COUPLING REACTIONS65 3.1 Introduction 66 3.2 Experimental 68 3.2.1 Materials and instrumentation 68 3.2.2 Catalytic studies on CC, CN cross coupling reactions 69 3.3 Results and discussions 71 3.3.1 Catalytic studies of Cu3(BTC)2 on CC cross coupling reaction (1) 71 3.3.2 Catalytic studies of Cu2(BDC)2(DABCO) on CC cross coupling reaction (2) 81 3.3.3 Catalytic studies of Cu2(BPDC)2(BPY) on CC cross coupling reaction (3) 93 3.3.4 Catalytic studies of Cu(BDC) on CN cross coupling reaction (4) 104 3.4 Conclusion 112 CHAPTER CONCLUSION 115 4.1 Summary of current work 115 4.2 Contributions of this thesis 116 LIST OF PUBLICATIONS 118 REFERENCES 120 APPENDICES 132 vi LIST OF FIGURES Figure 1.1 The 3D structures of representative MOFs [7] Figure 1.2 (a) Synthesis conditions commonly used for MOFs preparation; (b) indicative summary of the percentage of MOFs synthesized using various preparation routes [8] Figure 1.3 Development of MOF fields in comparison to the MOF catalysis in the last ten years (SciFinder until Jan 15, 2014) [25] Figure 1.4 Cu-MOFs (M=Cu, L=carboxylate) contain open metal sites that enable the reactivity of organic compounds in organic transformations Figure 1.5 Common coordination geometry of paddle wheel building units of Cu3(BTC)2, Cu2(BDC)2(DABCO), Cu2(BPDC)2(BPY), Cu(BDC) and their framework structures (L = Carboxylate linker, P = N-containing bidentate pillar linker and G = Guest molecule) [44-47] Figure 1.6 Reversible crystalline phase transformation of Cu(BDC) from the lamellar to the compact structure upon desorption/adsorption of DMF [40] 10 Figure 1.7 X-Ray structure of the doubly interpenetrating pillared-grid framework Cu2(BPDC)2(BPY) [45] 11 Figure 1.8 Pore apertures of Cu2(BDC)2(DABCO) [48] 12 Figure 1.9 Solvothermal synthesis of MOFs [10] 13 Figure 1.10 PXRD patterns of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [45-47, 52] 17 Figure 1.11 In situ PXRD patterns of Cu(BDC) [10] 18 Figure 1.12 SEM images of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [10, 33, 35, 37] 19 Figure 1.13 TGA of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [33, 35-37] 20 Figure 1.14 FT-IR spectra of Cu3(BTC)2, Cu(BDC), Cu2(BDC)2(DABCO) and Cu2(BPDC)2(BPY) [33, 35-37] 21 Figure 2.1 Structure of Cu3(BTC)2 (a) [46], Cu(BDC) (b) [44], Cu2(BDC)2(DABCO) [117] and Cu2(BPDC)2BPY [45] 40 Figure 2.2 X-ray powder diffractograms of the synthesized Cu3(BTC)2 44 Figure 2.3 FT-IR spectra of the Cu3(BTC)2 (a) and 1,3,5-benzenetricarboxylic acid (b) 45 Figure 2.4 SEM micrograph of the Cu3(BTC)2 46 Figure 2.5 TEM micrograph of the Cu3(BTC)2 46 Figure 2.6 TGA analysis of the Cu3(BTC)2 47 vii Figure 2.7 H2-TPR profile of the Cu3(BTC)2 48 Figure 2.8 X-ray powder diffractograms of the synthesized Cu2(BDC)2(DABCO) 49 Figure 2.9 SEM micrograph of the Cu2(BDC)2(DABCO) 50 Figure 2.10 TEM micrograph of the Cu2(BDC)2(DABCO) 50 Figure 2.11 FT-IR spectra of 1,4-benzenedicarboxylic acid (a), diazabicyclo[2.2.2]octane (b) and the Cu2(BDC)2(DABCO) (c) 51 Figure 2.12 TGA analysis of the Cu2(BDC)2(DABCO) 52 Figure 2.13 H2-TPR profile of the Cu2(BDC)2(DABCO) 53 Figure 2.14 X-ray powder diffractograms of the synthesized Cu2(BPDC)2(BPY) 54 Figure 2.15 TGA of the Cu2(BPDC)2(BPY) 55 Figure 2.16 SEM micrograph of the Cu2(BPDC)2(BPY) 56 Figure 2.17 TEM micrograph of the Cu2(BPDC)2(BPY) 56 Figure 2.18 FT-IR spectra of 4,4’-Biphenyldicarboxylic acid (a), 4,4’-Bipyridine (b) and the Cu2(BPDC)2(BPY) (c) 57 Figure 2.19 H2-TPR profile of the Cu2(BPDC)2(BPY) 58 Figure 2.20 X-ray powder diffractograms of the synthesized Cu(BDC) 59 Figure 2.21 TGA of the Cu(BDC) 60 Figure 2.22 SEM micrograph of the Cu(BDC) 61 Figure 2.23 TEM micrograph of the Cu(BDC) 61 Figure 2.24 FT-IR spectra of 1,4-benzenedicarboxylic acid (a) and the Cu(BDC) (b)62 Figure 2.25 H2-TPR profile of the Cu(BDC) 63 Figure 3.1 Effect of temperature on reaction conversions 73 Figure 3.2 Effect of catalyst amount on reaction conversions 73 Figure 3.3 Effect of phenylacetylene: N,N-dimethylaniline molar ratio on reaction conversions 74 Figure 3.4 Effect of oxidant on reaction conversions 74 Figure 3.5 Effect of oxidant concentration on reaction conversions 75 Figure 3.6 The selectivity of reaction with different oxidant concentrations on reaction conversions 75 Figure 3.7 Effect of different solvents on reaction conversions 75 Figure 3.8 The selectivity of reaction with different solvents on reaction conversions 75 Figure 3.9 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 76 Figure 3.10 Different Cu-MOFs catalysts for the direct CC coupling reactions 76 Figure 3.11 Catalyst recycling studies 78 Figure 3.12 FT-IR spectra of the fresh (a) and reused (b) Cu3(BTC)2 catalyst 79 Figure 3.13 X-ray powder diffractograms of the fresh (a) and reused (b) Cu3(BTC)2 catalyst 79 Figure 3.14 Effect of temperature on reaction conversions 82 viii Figure S20 1H NMR spectra a) and 13C NMR b) of N-(3-phenylprop-2nyl)benzenamine in CDCl3 N-(3-phenylprop-2-ynyl)benzenamine (B) Phenylacetylene (0.11 mL, 1.0 mmol), N-Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (diethyl ether/hexane = 1:20), 29 mg yellow oil was obtained (14 %) Rf = 0.27 1H NMR (500 MHz, CDCl3, ppm): δ = 7.40-7.38 (m, 2H), 7.29-7.27 (m, 3H), 7.24-7.21 (m, 2H), 6.80-6.77 (m, 1H), 6.74-6.72 (m, 1H), 4.15 (s, 2H), 4.00-3.90 (s, 1H) 13 C NMR (125 MHz, CDCl3, ppm): δ = 147.1, 131.7, 129.2, 128.2, 128.2, 122.9, 118.5, 113.6, 86.3, 83.3, 34.6 20 mmol scale reaction: Phenylacetylene (2.20 mL, 20 mmol), N-Methylaniline (4.40 mL, 40 mmol), Cu2(BDC)2(DABCO) (0.28 g, mol%), tert-butyl hydroperoxide (8.20 mL, 60 mmol), N,N-Dimethylacetamide (80 mL) After chromatography (diethyl ether/hexane = 1:20), 0.54 g yellow oil was obtained (13 %) 151 152 Figure S21 1H NMR spectra a) and 13C NMR b) of N-(3-(4-methoxyphenyl)prop-2yn-1-yl)-N-methylaniline in CDCl3 N-(3-(4-methoxyphenyl)prop-2-yn-1-yl)-N-methylaniline 4-ethynylanisole (0.13 mL, 1.0 mmol), N-Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,NDimethylacetamide (4 mL) After chromatography (diethyl ether/hexane = 1:20), 181 mg pale white solid was obtained (72 %) Rf = 0.26 1H NMR (500 MHz, CDCl3, ppm): δ = 7.31-7.24 (m, 4H), 6.90 (dd, J=8.0 Hz, J=1.0 Hz, 2H), 6.86-6.76 (m, 3H), 4.23 (s, 2H), 3.76 (s, 3H), 3.01 (s, 3H) 13C NMR (125 MHz, CDCl3, ppm): δ = 159.4, 149.4, 133.1, 129.0, 118.0, 115.2, 114.3, 113.8, 84.0, 83.5, 55.2, 43.3, 38.6 153 154 Figure S22 1H NMR spectra a) and 13C NMR b) of N-methyl-N-(3-(p-tolyl)prop-2-yn1-yl)aniline in CDCl3 N-methyl-N-(3-(p-tolyl)prop-2-yn-1-yl)aniline p-Tolylacetylene (0.11 mL, 1.0 mmol), N-Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (diethyl ether/hexane = 1:15), 167 mg yellow oil was obtained (71 %) Rf = 0.43 1H NMR (500 MHz, CDCl3, ppm): δ = 7.28-7.25 (m, 4H), 7.06 (d, J=8.0 Hz, 2H), 6.90 (dd, J=8.0 Hz, J=1.0 Hz, 2H), 6.80 (t, J=7.8 Hz, 1H), 4.24 (s, 2H), 3.03 (s, 3H), 2.31 (s, 3H) 13 C NMR (125 MHz, CDCl3, ppm): δ = 149.4, 138.1, 133.6, 129.1, 128.9, 120.0, 118.1, 114.4, 84.3, 84.2, 43.3, 38.7, 21.4 155 156 Figure S23 1H NMR spectra a) and 13C NMR b) of N-methyl-N-(non-2-yn-1yl)aniline in CDCl3 N-methyl-N-(non-2-yn-1-yl)aniline 1-octyne (0.15 mL, 1.0 mmol), N- Methylaniline (0.22 mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tertbutyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (used hexane as eluent), 133 mg yellow oil was obtained (58 %) Rf = 0.3 1H NMR (500 MHz, CDCl3, ppm): δ = 7.26-7.25 (m, 2H), 6.85 (d, J=8.0 Hz, 2H), 6.78 (t, J=7.5 Hz, 1H), 4.00 (s, 2H), 2.95 (s, 3H), 2.14-2.11 (m, 2H), 1.45-1.42 (m, 2H), 1.33-1.21 (m, 6H), 0.86 (t, J=7.0 Hz , 3H) 13C NMR (125 MHz, CDCl3, ppm): δ = 149.5, 129.0, 117.9, 114.3, 84.5, 75.3, 42.9, 38.5, 31.3, 28.7, 28.4, 22.5, 18.7, 14.0 157 Figure S24 1H NMR spectra of 4-methoxy-N-methyl-N-(3-phenylprop-2-yn-1yl)aniline in CDCl3 4-methoxy-N-methyl-N-(3-phenylprop-2-yn-1-yl)aniline (0.11 mL, 1.0 mmol), N-methyl-p-anisidine (0.274g, Phenylacetylene 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (ethyl acetate/hexane = 1: 9), 181 mg yellow oil was obtained (72 %) Rf =0.27 1H NMR (300 MHz, CDCl3, ppm): δ = 7.40-7.28 (m, 5H), 6.97-6.86 (m, 4H), 4.19 (s, 2H), 3.79 (s, 3H), 2.98 (s, 3H) 158 Figure S25 1H NMR spectra of 4-chloro-N-methyl-N-(3-phenylprop-2-yn-1yl)aniline in CDCl3 4-chloro-N-methyl-N-(3-phenylprop-2-yn-1-yl)aniline (0.11 mL, 1.0 mmol), 4-cloro-N-Methylaniline (0.24 Phenylacetylene mL, 2.0 mmol), Cu2(BDC)2(DABCO) (0.014g, mol%), tert-butyl hydroperoxide (0.41 mL, 3.0 mmol), N,N-Dimethylacetamide (4 mL) After chromatography (diethyl ether/ hexane = 1: 15), 196 mg yellow oil was obtained (77 %) Rf = 0.43 1H NMR (300 MHz, CDCl3, ppm): δ = 7.38 (dd, J=6.6 Hz, J=3.0 Hz, 2H), 7.29 -7.22 (m, 5H), 6.84 (d, J=9.3 Hz, 2H), 4.25 (s, 2H), 3.03 (s, 3H) 159 Reaction (3) 160 Figure S26 1H NMR a) and 13C NMR spectra b) of 2-benzyl-1-(phenylethynyl)1,2,3,4-tetrahydroisoquinoline in CDCl3 2-benzyl-1-(phenylethynyl)-1,2,3,4-tetrahydroisoquinoline Phenylacetylene (0.11 mL, 1.0 mmol), Benzaldehyde (0.11 mL, 1.1 mmol), Tetrahydroisoquinoline (0.141 mL, 1.1 mmol), Cu2(BPDC)2(BPY) (0.020g, mol%), toluene (4 mL) After chromatography (ethyl acetate/hexane = 1:20), 281mg colorless oil was obtained (87 %) Rf = 0.30 1H NMR (500 MHz, CDCl3, ppm): δ = 7.47-7.42 (m, 4H), 7.33 (t, J=7.5 Hz, 2H), 7.29-7.22 (m, 5H), 7.18-7.11 (m, 3H), 4.79 (s, 1H), 3.95 (d, J=13.0 Hz, 1H), 3.91 (t, J=13.0 Hz, 1H), 3.11-2.99 (m, 2H), 2.84-2.77 (m, 2H) 13C NMR (125 MHz, CDCl3, ppm): δ = 138.3, 135.5, 134.1, 131.8, 129.3, 129.0, 128.3, 128.2, 128.0, 127.8, 127.2, 126.9, 125.8, 123.3, 87.5, 86.8, 59.6, 54.4, 45.8, 29.0 161 Figure S27 HMBC spectrum of 2-benzyl-1-(phenylethynyl)-1,2,3,4tetrahydroisoquinoline in CDCl3 162 Reaction (4) Cu(BDC) CuCl2.2H2O CuCl Cu(NO3)2 Conversion (%) 100 80 60 40 20 0 30 60 90 120 150 180 Time (min) Figure S28 Different copper salts as catalyst for the quinoxaline synthesis reaction 163 164 Figure S29 1H NMR spectra a) and 13C NMR b) of 2-phenylquinoxaline in CDCl3 2-phenylquinoxaline -hydroxyacetophenone (0.136 g, 1.0 mmol), phenylenediamine (0.119 g, 1.1 mmol), Cu(BDC) (0.010g, mol%) After chromatography (dichloromethane/hexane = 2:1), 196 mg yellow solid was obtained (95 %) Rf =0.3 This compound is known 1H NMR (500 MHz, CDCl3, ppm): δ = 9.31 (s, 1H), 8.19 (dd, J = 7.0 Hz, J = 1.5 Hz, 1H), 8.15 (dd, J = 8.3 Hz, J = 1.3 Hz, 1H), 8.11 (dd, J = 8.3 Hz, J = 1.3 Hz, 1H), 7.78-7.71 (m, 2H), 7.57-7.49 (m, 3H) 13C NMR (125 MHz, CDCl3, ppm): δ = 151.8, 143.3, 142.2, 141.5, 136.7, 130.2, 130.1, 129.6, 129.5, 129.1, 129.1, 127.5 165 ... heterogeneous catalysts for direct C? ? ?C and C? ? ?N coupling reactions These Cu- MOFs were found to be highly catalytically active for direct C? ? ?C and C? ? ?N coupling reactions The CuMOF catalysts could be recovered... 1.2 Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) 1.2.1 Structures and properties of Cu3 (BTC)2, Cu( BDC), Cu2 (BDC)2(DABCO) and Cu2 (BPDC)2(BPY) Cu3 (BTC)2 [46], Cu( BDC) [44], Cu2 (BDC)2(DABCO)... demand of recyclable heterogeneous catalysts for these important transformations 1.3 C? ? ?C cross coupling reactions The Carbon-Carbon (C? ? ?C) cross coupling reactions play an important role in organic