using metal-organic framework Cu-MOF-74 as an efficient heterogeneous catalyst Hanh T. H. Nguyen, Oanh T. K. Nguyen, Thanh Truong *, Nam T. S.

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Synthesis of imidazo[1,5-a]pyridines via oxidative amination of C(sp 3 )-H bond under air using metal-organic framework Cu-MOF-74 as an efficient heterogeneous catalyst Hanh T. H. guyen, Oanh T. K. guyen, Thanh Truong *, am T. S. Phan * Department of Chemical Engineering, HCMC University of Technology, VU-HCM, 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Viet am * tvthanh@hcmut.edu.vn, ptsnam@hcmut.edu.vn Ph: (+84 8) ext Fx: (+84 8) Supporting Information Relative intensity Theta scale Fig. S1. X-ray powder diffractograms of the Cu-MOF-74. 1

2 Fig. S2. SEM micrograph of the Cu-MOF-74. 2

3 Fig. S3. TEM micrograph of the Cu-MOF-74. 3

4 dv/dw(cm3/g. Å) Pore width(å) Fig. S4. Pore size distribution of the Cu-MOF-74. 4

5 250 Quantity absorbed(cm3/g STP) Relative presure(p/po) Fig. S5. itrogen adsorption/desorption isotherm of the Cu-MOF-74. Adsorption data are shown as closed circles and desorption data as open circles. 5

6 Weight (%) Weight loss (%) DTG Temperature ( C) DTG( D%Weigt loss/ o C) Fig. S6. TGA analysis of the Cu-MOF-74. 6

7 a) Transmittance (%) b) Wavenumber (cm -1 ) Fig. S7. FT-IR spectra of terephthalic acid (a), and the Cu-MOF-74 (b). a) b) Fig. S8. Particles size distribution of non-grinded (a) and grinded (b) Cu MOF-74 7

8 Fig. S9. 1 H-MR spectra of 1,3-diphenylimidazo[1,5-a]pyridine. 8

9 Fig. S C-MR spectra of 1,3-diphenylimidazo[1,5-a]pyridine. Characterization data for 1,3-diphenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:8): yellow solid, 70% yield. This compound is known [1]. 1 H-MR (500 MHz, CDCl 3 ) δ 8.22 (d, J=7.5 Hz, 1H), 7.95 (s, 1H), 7.93 (s, 1H), (m, 3H), (m, 5H), (m, 1H), (m, 1H), 6.55 (t, J=6.8 Hz, 1H); 13 C-MR (125 MHz, CDCl 3 ) δ , , , , 130.0, , , , , , , , , ,

10 Cl Fig. S11. 1 H-MR spectra of 3-(2-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine. 10

11 Cl Fig. S C-MR spectra of 3-(2-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(2-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:4): yellow oil, 53% yield. 1H-MR (500 MHz, CDCl3) δ 7.95 (d, J= 7.5 Hz, 2H), 7.89 (d, J= 9 Hz, 1H), 7.68 (m, 1H), 7.6 (d, J= 7.5, 1H), 7.56 (m, 1H), (m, 4H), (m, 1H), (m, 1H), 6.61 (t, J= 6.8Hz, 1H); 13C-MR (125 MHz, CDCl3) δ , , , , 131.8, , , , , , , , , , ,

12 Cl Fig. S13. 1 H-MR spectra of 3-(3-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine. 12

13 Cl Fig. S C-MR spectra of 3-(3-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(3-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:2): yellow oil, 54% yield. This compound is known [1]. 1 H-MR (500 MHz, CDCl 3 ) δ 8.21 (d, J= 7.5 Hz, 1H), 7.92 (s, 1H), 7.9 (s, 1H), (m, 2H), (m, 1H), (m, 4H), (m, 1H), (m, 1H), 6.61 (m, 1H); 13 C-MR (125 MHz, CDCl 3 ) δ 136.6, , , , , , , , , , , , , , , ,

14 Cl Fig. S15. 1 H-MR spectra of 3-(4-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine. 14

15 Cl Fig. S C-MR spectra of 3-(4-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(4-chlorophenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:8): yellow solid, 53% yield. This compound is known [2] 1 H-MR (500 MHz, CDCl 3 ) δ 8.20 (d, J= 7 Hz, 1H), 7.93 (s, 1H), 7.92 (s, 1H), 7.86 (d, J= 9.5 Hz, 1H), (m, 2H), (m, 4H), (m, 1H), (m, 1H), 6.62 (t, J= 6.5 Hz, 1H); 13 C-MR (125 MHz, CDCl 3 ) δ , , , , , , , , , , ,

16 OCH 3 Fig. S17. 1 H-MR spectra of 3-(2-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine. 16

17 OCH 3 Fig. S C-MR spectra of 3-(2-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(2-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:14): yellow oil, 61% yield. This compound is known [3]. 1 H-MR (500 MHz, CDCl 3 ) δ 7.96 (s, 1H), 7.94 (s, 1H), 7.80 (d, J= 9.5 Hz, 1H), (m, 1H), 7.53 (d, J= 8 Hz, 1H), (m, 3H), (m, 1H), (m, 1H), 6.99 (d, J= 8.5 Hz, 1H), (m, 1H), (m, J= 7 Hz, 1H), 3.74 (s, 3H); 13 C-MR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , ,

18 OCH 3 Fig. S19. 1 H-MR spectra of 3-(3-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine. 18

19 OCH 3 Fig. S C-MR spectra of 3-(3-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(3-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:2): yellow oil, 70% yield. This compound is known [3]. 1 H-MR (500 MHz, CDCl 3 ) δ 8.26 (d, J= 7 Hz, 1H), 7.94 (s, 1H), 7.93 (s, 1H), 7.84 (d, J= 9.5 Hz, 1H), (m, 5H), (m, 1H), (m, 1H), (m, 1H), (m, J= 7.3 Hz, 1H), 3.89 (s, 3H); 13 C-MR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , ,

20 OCH 3 Fig. S21. 1 H-MR spectra of 3-(4-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine. 20

21 OCH 3 Fig. S C-MR spectra of 3-(4-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(4-methoxyphenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:1): yellow solid, 73% yield. This compound is known [4]. 1 H-MR (500 MHz, CDCl 3 ) δ 8.16 (d, J= 7.5 Hz, 1H), (m, 2H), 7.82 (d, J= 9.5 Hz, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 3.88 (s, 3H); 13 C-MR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , ,

22 H 2 Fig. S23. 1 H-MR spectra of 3-(4-aminophenyl)-1-phenylimidazo[1,5-a]pyridine. 22

23 H 2 Fig. S C-MR spectra of 3-(4-aminophenyl)-1-phenylimidazo[1,5-a]pyridine. 23

24 Fig. S25. HRMS (EIS+) of 3-(4-aminophenyl)-1-phenylimidazo[1,5-a]pyridine. Characterization Data for 3-(4-aminophenyl)-1-phenylimidazo[1,5-a]pyridine Prepared as shown in the general experimental procedure and purified on silica gel (ethyl acetate/hexane = 1:1): light orange solid, 67% yield. 1 H-MR (500 MHz, CDCl 3 ) δ 8.13 (d, J = 7 Hz, 1H), 7.92 (d, J = 7 Hz, 2H), 7.79 (d, J = 9.5 Hz, 1H), 7.59 (d, J = 8.5 Hz, 2H), 7.45 (t, J = 7.5 Hz, 2H), 7.28 (t, J = 7.5 Hz, 1H), 6.79 (d, J = 8.5 Hz, 2H), 6.72 (dd, J = 9, 6.5 Hz, 1H), 6.50 (t, J = 6.8 Hz, 1H), 3.88 (s, 2H). 13 C-MR (125 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , HRMS (EIS+): Calculated for C 19 H 15 3 [M+H] , Found

25 Table S1. Optimization of reaction conditions. Entry Temperature Catalyst Reactant molar Solvent Yield (%) ( o C) concentration ratio (mol%) 1 RT 10 1:3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :3 DMF :1 DMF :2 DMF :3 DMF :4 DMF :3 MA :3 MP :3 toluene 58 25

26 :3 chlorobenzene :3 DMF :3 DMSO :3 n-butanol :3 p-xylene :3 benzonitrile :3 tert-butanol 44 Table S2. Different catalysts for the condensation-cyclization reaction a. Entry Homogeneous catalyst Heterogeneous catalyst Yield (%) 1 Cu(O 3 ) CuCl CuSO Cu(OAc) Cu(acac) CuBr CuBr 29 8 CuI 28 9 CuCl Co(OAc) Zn(OAc) Mn(OAc)

27 13 i(oac) AgOAc ,5-dihydroxyterephthalic acid Cu(BDC) Cu 2 (BDC) 2 (DABCO) Cu 3 (BTC) Cu 2 (BPDC) 2 (BPY) Cu(OBA) Cu 2 (OBA) 2 (BPY) Cu(IA) Cu-MOF a : The reaction was then carried out in DMF under air at 120 o C for 8 h, using 3 equivalents of benzylamine, in the presence of 10 mol% catalyst, at 2-benzoyl pyridine concentration of 0.2 M. References 1. M. Li, Y. Xie, Y. Ye, Y. Zou, H. Jiang, W. Zeng, Org. Lett. 16 (2014) H. Wang, W. Xu, Z. Wang, L. Yu, K. Xu, J. Org. Chem. 80 (2015) A. Joshi, D. C. Mohan, S. Adimurthy, Org. Lett., 18 (2016), J.M. Crawforth, M. Paoletti, Tetrahedron Lett. 50 (2009)