Supporting Information Pd()-Catalyzed Decarboxylative Coupling and Tandem C H Arylation/Decarboxylation for the Synthesis of Heteroaromatic Biaryls Debkumar andi, Yang-Ming Jhou, Jhen-Yi Lee, Bing-Chiuan Kuo, Chien-Yu Liu, Pei-Wen Huang and Hon Man Lee* Department of Chemistry, ational Changhua University of Education, Changhua 558, Taiwan, R..C. E-mail: leehm@cc.ncue.edu.tw Table of Content 1. Details of X-ray Diffraction Studies S2 2. Crystallographic Data for 1, 6, 17A, 17B, 21A and 23A S3 S4 3. Catalytic Table S4 4. X-ray Structures for 1, 6, 17A, 17B, 21A and 23A S5 S7 5. Proposed Catalytic Cycles S8 6. Copies of MR spectra S9 S27 S1
X-Ray Diffraction Studies. Compound 1 was collected at 1(2) K on with a CCD area detector. Graphite-monochromatized Mo Kα radiation was used (λ =.7173 Å). Data collection and reduction were performed using CrysAlisPro software. 1 Single-crystal X-ray diffraction data for all others were collected with a CCD area detector and a graphite monochromater utilizing Mo Kα radiation (λ =.7173 Å) at 15(2) K. The unit cell parameters were obtained by least-squares refinement. The data were integrated via SAIT. 2 Lorentz and polarization effect and multiscan absorption corrections were applied with SADABS. 3 The structures were solved by direct methods and refined by full-matrix least squares methods against F 2 with SHELXTL. 4 All non-h atoms were refined anisotropically. All H-atoms were fixed at calculated positions and refined with the use of a riding model. CCDC-882516 (1), -88252 (6), -882517 (17A), -882768 (17B), -882518 (21A), and -882519 (23A) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. S2
Table S1. Crystallographic Data empirical formula 1 C 4 H 8.5C 6 H 14 6 17A 17B 21A 23A C 46 H 48 6 5 Pd C 15 H 12 2 C 16 H 12 2 C 16 H 12 2 C 19 H 15 C 16 H 15 C 4 H 8.5C 6 H 14 formula weight 964.95 236.27 232.28 232.28 257.32 221.29 crystal system monoclinic triclinic monoclinic orthorhombic monoclinic orthorhombic space group P2 1 /n Pī P2 1 /n P2 1 2 1 2 1 P2 1 /c P2 1 2 1 2 1 a, Å 16.1631(3) 6.8234(2) 7.8322(2) 7.94(3) 1.3353(2) 7.243(15) b, Å 17.294(4) 9.2369(2) 17.51(4) 1.3688(4) 19.1288(4) 9.93(2) c, Å 18.568(3) 9.4964(2) 9.8396(2) 16.6945(8) 7.464(1) 17.387(4) α, deg 9 8.78(1) 9 9 9 9 β, deg 16.224(2) 74.517(1) 111.932(1) 9 97.652(1) 9 γ, deg 9 79.485(1) 9 9 9 9 V, Å 3 4822.61(16) 563.9(2) 1218.95(5) 1227.99(9) 138.68(4) 1246.7(5) T, K 1(2) 15(2) 15(2) 15(2) 15(2) 15(2) D, g/cm 3 1.329 1.393 1.266 1.256 1.238 1.179 Z 4 2 4 4 4 4 no. of unique data 1377 2849 3158 318 355 3221 no. of params refined 591 164 164 164 181 157 R 1 a [I > 2σI].465.424.467.368.48.435 wr 2 b (all data).1468.1145.1253.868.1136.1234 a R 1 = Σ( F o F c )/Σ F o. b wr 2 = [Σ( F o 2 F c 2 ) 2 /Σ (F o 2 )] 1/2 S3
Table S2. Selected bond distances (Å) and Angles ( ) of 1 1 Pd1 C1 2.52(4) Pd1 C23 2.66(3) Pd1 C24 2.87(4) Pd1 C25 2.124(4) C1 Pd1 C23 96.31(13) C1 Pd1 C24 111.63(15) C23 Pd1 C25 111.74(14) C24 Pd1 C25 4.25(15) C1 Pd1 C25 151.85(14) C23 Pd1 C24 151.92(15) Table S3. Tandem C H arylation and decarboxylation of 1-methylindole-3-carboxylic acid and aryl halides mediated by different catalyst systems a entry cat. yield (%) c 15A:15C 1 1 6 -- 2 1 b 6 3:1 3 Pd(Ac) 2/2L HCl 22 -- 4 Pd(Ac) 2/2PCy 3 37 4:1 5 Pd(PPh 3) 4 46 -- a Reaction conditions: 3. mmol 2', 3. mmol 4-bromoacetophenone, 6. mmol KAc, 4 ml dry DMA, 2.5 mol % 1, 16 ºC, isolated yield, 24 h, L HCl = ligand precursor in 1. b 3 equiv. 4-bromoacetophenone. c isolate yield. S4
Figure S1. Molecular structure of 1 (5% probability level) Figure S2. Molecular structure of 6 (5% probability level) S5
Figure S3. Molecular structure of 17A (5% probability level) Figure S4. Molecular structure of 17B (5% probability level) S6
Figure S5. Molecular structure of 21A (5% probability level) Figure S6. Molecular structure of 23A (5% probability level) S7
Me F PdL 2 Me CH F Me PdLH Me CPdLH F F Scheme S1. A proposed catalytic cycle for the decarboxylation mediated by 1 Scheme S2. A proposed catalytic cycle for the decarboxylation coupling mediated by 1 S8
MESITYL CH3 LIGAD PRECURSR H.ESP 2.3 1..9.8 ormalized Intensity.7.6.5.4 + 6.95 Cl - 3.29 2.29.3.2 1.49 7.56 7.54 7.36 7.48 7.5 5.53.1 1.1 6.43 1.2 2.3 2.7 3.17 3.116.24 11 1 9 8 7 6 5 4 3 2 Figure S7. 1 H MR spectrum of [LH] + Cl - 1. MESITYL CH3 LIGAD PRECURSR C13.ESP 134.27 129.6 77.57 77.15 76.72.9 17.35.8.7 + Cl - 2.98 ormalized Intensity.6.5.4.3.2 164.32 141. 14.81 127.64 124.5 122.4 51.7 37.79.1 24 22 2 18 16 14 12 1 8 6 4 2 Figure S8. 13 C{ 1 H} MR spectrum of [LH] + Cl - S9
MESITYL PD() CH3 CMPLEX H.ESP 1.59 1..9.8 R R ormalized Intensity.7.6.5.4 7.24 Pd R = mesityl.3.2.1 7.57 7.55 7.43 7.29 7.26 6.97 6.89 6.88 6.71 6.61 6.56 6.8 5.18 5.12 4.43 4.37 4.9 4.3 3.31 3.2 3.5 2.99 2.33 2.23 2.7 1.67 1.43.5 6.61 4.58 1.55 2.2 1.53 2.42 1.3 1.48 1.3 1.9 1.8 3.15 1.53 3.511.42 1.543.6 3.19 3.32 3.71 3.34 3.62 11 1 9 8 7 6 5 4 3 2 1 Figure S9. 1 H MR spectrum of 1 MESITYL PD() CH3 CMPLEX C13 44-5.ESP 77.43 77. 76.58.7.65.6.55 R R.5 ormalized Intensity.45.4.35.3.25 Pd R = mesityl.2.15.1.5 193.7 188.66 174.13 173.9 166.53 166.24 141.74 138.9 138. 136.75 135.18 13.46 129.91 127.92 127. 123.18 122.64 121.97 53.26 51.16 39.27 38.9 38.71 37.16 21.14 21.5 17.44 17.32 2 18 16 14 12 1 8 6 4 2 Figure S1. 13 C{ 1 H} MR spectrum of 1 S1
1. complex 2.esp 7.41 7.33.9.8.7 ormalized Intensity.6.5.4.3 7.88 7.86 6.89 6.91 6.86 6.49 6.51 6.47.2.1 1.2 3. 1.1 1.1 1.5 1. 9.5 9. 8.5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 Figure S11. 1 H MR spectrum of 2 1. complex 3.esp 2.44.9 F.8.7 ormalized Intensity.6.5.4.3 7.76 7.74 7.73 7.13 7.1 6.22.2 7.72 7.71 7.8 7.7.1 2.5 2.28 1. 3.16 9 8 7 6 5 4 3 2 1 Figure S12. 1 H MR spectrum of 3 S11
complex 4.ESP 3.88 1..9.8.7 ormalized Intensity.6.5.4.3.2.1 7.84 7.82 7.49 7.47 7.41 7.18 7.17 7.17 6.67 1.3 2.16 1.11 1. 1. 3.17 1 9 8 7 6 5 4 3 2 1 Figure S13. 1 H MR spectrum of 4 1. complex 5.esp.9.8.7 ormalized Intensity.6.5.4.3.2.1 7.66 7.64 7.31 7.29 7.26 7.12 7.11 7.1 7.9 7.9 6.55 6.54 5.32 1. 9.61 1. 2.1 1. 9.5 9. 8.5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. Figure S14. 1 H MR spectrum of 5 S12
1. complex 6.esp 2.62.9.8 ormalized Intensity.7.6.5.4.3 8.8 8.5 7.77 7.67 7.64.2.1 8.39 7.24 7.22 6.82 6.85 1.2 2.4 1.25 3. 1.24 1.1 3.28 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 Figure S15. 1 H MR spectrum of 6 complex 7.esp 7.74 1. 7.65.9 ormalized Intensity.8.7.6.5.4.3.2 8.34 8.31 7.76 7.75 7.63 7.63 7.63 7.25 7.19 7.22 6.88 6.85 6.83.1 1. 6.75 1.16 1.6 12 11 1 9 8 7 6 5 4 3 2 Figure S16. 1 H MR spectrum of 7 S13
1. complex 8.esp 7.4.9 7.41.8.7 7.57 ormalized Intensity.6.5.4 7.59 7.37.3 8.2 8.18 7.35 7.35 7.28 6.67 6.67.2 7.9 7.6 7.4 6.65 6.64.1 1.29 7. 1.18 1.22 1 9 8 7 6 5 4 3 2 1 Figure S17. 1 H MR spectrum of 8 1. complex 9.esp 2.3.9.8.7 ormalized Intensity.6.5.4.3.2.1 8.17 7.56 7.58 7.58 7.55 7.31 7.29 7.2 7.17 7.4 6.66 6.64 6.62 1.3 2.61 4.56 1.9.98 3.4 11 1 9 8 7 6 5 4 3 2 1 Figure S18. 1 H MR spectrum of 9 S14
complex 1.esp 3.71 1..9.8 CH 3.7 ormalized Intensity.6.5.4 7.58.3.2.1 8.22 8.19 7.54 7.51 7.5 7.27 7. 6.96 6.95 6.94 6.82 6.63 6.61 1.11 1.19 1.3 1.16 3.35 1.7 1.5 3. 1 9 8 7 6 5 4 3 2 Figure S19. 1 H MR spectrum of 1 1. complex 11.esp 2.59 2.44.9.8 F.7 ormalized Intensity.6.5.4.3 7.95 7.92 7.25 7.22 6.98.2 7.38 7.36 7.35 7.1 6.95.1 2.62.1 2.3 2. 3.54 3.48 11 1 9 8 7 6 5 4 3 2 1 Figure S2. 1 H MR spectrum of 11 S15
1. complex 11-C13.esp.9.8 F.7 ormalized Intensity.6.5.4.3.2.1 197.56 167.25 165.19 161.89 16.24 136.29 135.22 13.45 13.35 129.87 127.48 128.82 124.79 115.98 115.69 114.9 26.67 11.76 24 22 2 18 16 14 12 1 8 6 4 2 Figure S21. 13 C{ 1 H} MR spectrum of 11 complex 12.esp 2.43 1..9 F.8.7 ormalized Intensity.6.5.4.3 7.64 7.61 7.26 7.24 6.98.2 6.95.1 2.7 4.21 2. 3.2 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1-1 Figure S22. 1 H MR spectrum of 12 S16
1. complex 12-C13.esp.9.8.7 F 132.63 ormalized Intensity.6.5.4.3.2.1 167.48 161.98 16.15 135.22 13.31 127.97 124.47 118.43 116.13 114.38 115.83 111.69 11.79 18 16 14 12 1 8 6 4 2 Figure S23. 13 C{ 1 H} MR spectrum of 12 1. complex 13.esp.9.8 H 3 C.7 ormalized Intensity.6.5.4 F 3.68 2.27.3.2.1 7.3 7.28 7.27 7.25 6.94 6.91 6.85 6.77 6.74 2. 2.152.15 2.7 3.36 3.15 11 1 9 8 7 6 5 4 3 2 1 Figure S24. 1 H MR spectrum of 13 S17
.8 complex 13-C13.esp.7 H 3 C.6 ormalized Intensity.5.4.3 F 13.97 114.28.2.1 166.55 165.4 161.74 16.29 159.18 13.35 13.24 125.41 115.74 115.45 55.29 29.73 18 16 14 12 1 8 6 4 2 Figure S25. 13 C{ 1 H} MR spectrum of 13 1. complex 14.esp 2.42.9 F.8.7 ormalized Intensity.6.5.4.3.2.1 7.35 7.43 7.41 7.38 7.37 7.16 6.98 6.95 5.54 2.74 2. 3.88 12 11 1 9 8 7 6 5 4 3 2 1-1 Figure S26. 1 H MR spectrum of 14 S18
1. complex 15A.esp 3.77 2.65.9.8 ormalized Intensity.7.6.5.4.3.2.1 8.6 8.3 7.66 7.63 7.62 7.6 7.36 7.28 7.16 7.13 6.65 2.24 3.41 1.37 1.44 1.2 1. 3.16 3.3 13 12 11 1 9 8 7 6 5 4 3 2 1 Figure S27. 1 H MR spectrum of 15A complex 15B.esp 4.9 1. 2.64.9.8.7 ormalized Intensity.6.5.4.3 8.6 8.3 7.72 7.69 7.46 7.39 7.24.2.1 7.18 7.17 7.15 7.14 2. 3.25 1.25 2.51 1.1 3.38 3.16 13 12 11 1 9 8 7 6 5 4 3 2 Figure S28. 1 H MR spectrum of 15B S19
1. complex 15C.esp 3.7 2.63 2.57.9.8.7 ormalized Intensity.6.5.4.3 7.99 7.96 7.87 7.85 7.43 7.36 7.33.2 7.45 7.24 7.22.1 2.23 2.19 1.6.88 1.24 3.24 3.72 3.71 11 1 9 8 7 6 5 4 3 2 1 Figure S29. 1 H MR spectrum of 15C complex 15c-C13.esp 128.59 1..9.8 ormalized Intensity.7.6.5.4.3.2 197.83 197.65 14.29 137.82 136.6 136.33 131.32 129.72 123.1 121.1 119.56 115.5 11.1 31.22 26.74 26.58.1 24 22 2 18 16 14 12 1 8 6 4 2 Figure S3. 13 C{ 1 H} MR spectrum of 15C S2
complex 16.esp 2.6 1..9.8.7 ormalized Intensity.6.5.4.3 7.97 7.95 7.27 7.55 7.52 7.2 7.5 7.19 7.4 6.75 5.38.2.1 7.71 7.31 2.2 1.34 2.56.28 2.53 1. 2.12 3.23 1 9 8 7 6 5 4 3 2 1 Figure S31. 1 H MR spectrum of 16A complex 16A-C13.esp.3.25 ormalized Intensity.2.15.1 128.96 128.84 128.59 125.8.5 197.58 14.43 138.55 137.81 137.27 122.59 12.83 12.45 11.6 13.59 47.88 29.66 24 22 2 18 16 14 12 1 8 6 4 2 Figure S32. 13 C{ 1 H} MR spectrum of 16A S21
complex 17A.esp 3.76 1..9.8 ormalized Intensity.7.6.5.4.3.2.1 7.75 7.72 7.62 7.6 7.32 7.6 7.37 7.3 7.17 7.14 6.65 2.81 3.45 1.48 1.28 1. 1.7 3.6 11 1 9 8 7 6 5 4 3 2 Figure S33. 1 H MR spectrum of 17A complex 17B.esp 3.85 1..9.8.7 ormalized Intensity.6.5.4 7.72 7.68 7.33.3.2.1 7.92 7.9 7.75 7.4 7.37 7.31 7.24 7.23 7.2 1. 4.65 4.81 3.46 12 11 1 9 8 7 6 5 4 3 2 Figure S34. 1 H MR spectrum of 17B S22
1. complex 17B-C13.esp.9.8.7 ormalized Intensity.6.5.4 132.16 126.61.3.2.1 14.19 137.22 127.38 125.11 122.13 12.3 119.14 119.5 114.48 19.5 17.96 32.68 17 16 15 14 13 12 11 1 9 8 7 6 5 4 3 2 1 Figure S35. 13 C{ 1 H} MR spectrum of 17B 1. complex 18A.esp.9.8.7 ormalized Intensity.6.5.4.3.2 7.7 7.67 7.65 7.65 7.63 7.53 7.5 7.27 7.2 7.1 6.74 5.35.1 3.45 2.5 6.37 2.4 1. 2.11 11 1 9 8 7 6 5 4 3 2 Figure S36. 1 H MR spectrum of 18A S23
.8 complex 18A-C13.esp.7.6 ormalized Intensity.5.4.3.2.1 139.56 137.61 137.23 132.39 129.37 128.99 127.51 125.78 123.3 121.5 12.7 118.72 111.37 11.7 14.21 47.96 16 15 14 13 12 11 1 9 8 7 6 5 4 Figure S37. 13 C{ 1 H} MR spectrum of 18A complex 19.esp 3.75 1..9.8.7 ormalized Intensity.6.5.4.3 7.5 7.5 7.46 7.24 6.56.2.1 7.65 7.62 7.35 7.16 7.14 7.11 1.8 6.62 1.59 1.61. 3.17 1 9 8 7 6 5 4 3 2 1 Figure S38. 1 H MR spectrum of 19A S24
complex 2.esp Water 3.89 1..9 H 3 C.8 CH 3 ormalized Intensity.7.6.5.4 H 3 C 6.7 3.91 3.75.3.2.1 7.63 7.6 7.34 7.24 7.22 7.13 6.53 1.8 1. 1.81 1.4 2.29 1.8 9.5 3.66 11 1 9 8 7 6 5 4 3 2 Figure S39. 1 H MR spectrum of 2A 1. comokex 2A-C13.esp.9.8 H 3 C ormalized Intensity.7.6.5.4 H 3 C CH 3 16.71 56.26.3.2.1 153.21 141.55 138.25 137.98 128.38 127.83 121.77 12.44 119.99 19.63 11.44 61.3 31.24 18 16 14 12 1 8 6 4 2 Figure S4. 13 C{ 1 H} MR spectrum of 2A S25
1. complex 21A.esp 3.51.9.8.7 ormalized Intensity.6.5.4.3.2.1 7.96 7.96 7.95 7.74 7.72 7.98 7.97 7.57 7.56 7.45 7.42 7.32 7.22 7.2 7.2 6.66 2.21 2.13 5.57 1.15 1.18 1. 3.15 1.5 1. 9.5 9. 8.5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. 3.5 3. 2.5 2. Figure S41. 1 H MR spectrum of 21A complex 22.esp 3.87 1. 3.77.9.8.7 ormalized Intensity.6.5.4 H 3 C.3.2 6.59 7.67 7.64 7.4 7.37 7.16 7.13 7.8 6.97 7.7.1 1.3 2.26 1.33.41 1.11 1. 3.78 3.3 1 9 8 7 6 5 4 3 2 Figure S42. 1 H MR spectrum of 22A S26
complex 23A.esp 3.73 1..9.8 2.42 ormalized Intensity.7.6.5.4.3 7.42 7.39 7.29 7.26 7.24 6.53.2.1 7.64 7.61 7.16 7.15 7.11 7.13 1.9 6.53 1. 1.1 3.12 3.47 11 1 9 8 7 6 5 4 3 2 1 Figure S43. 1 H MR spectrum of 23A References 1. CrysAlisPro. xford Diffraction Ltd., Abingdon, England, 29. 2. R. A. Hughes and C. J. Moody, Angew. Chem. Int. Ed., 27, 46, 793-7954. 3. G. M. Sheldrick, SADABS. University of Göttingen, Germany, 1996. 4. G. Sheldrick, Acta Crystallogr., 28, A64, 112-122. S27