Supporting Information Co(III)-Catalyzed C H Activation: A Site-Selective Conjugate Addition of Maleimide to Indole at the C-2 Position Nachimuthu Muniraj and Kandikere Ramaiah Prabhu* Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka, India *E-mail: prabhu@orgchem.iisc.ernet.in S-1
Contents 1 Deuterium labelling studies S-3 2 1 H and 13 C NMR spectra for all the products S-5 S-2
Deuterium labeling studies: Scheme S1: Deuterium labeling studies In a 8-mL screw cap reaction vial, N-pyrimidinylindole (0.2 mmol), cobalt catalyst (5mol %) and AgOAc (10 mol %), were added followed by the addition of TFE:MeOD(2 ml, 9:1). This vial was sealed with a screw cap, placed in a pre-heated metal block at 100 C for 2 h, cooled to room temperature, and concentrated to yield the crude product, which was further purified by flash chromatography to give the desired product deutrio-1a in 99% yield. The deuterium incorporation was calculated from 1 H NMR spectroscopy (See the following 1 H NMR spectra). S-3
11 10 9 8 7 6 5 4 3 2 1 ppm 8.848 8.827 8.697 8.685 8.302 8.292 7.662 7.660 7.641 7.392 7.389 7.374 7.372 7.369 7.354 7.351 7.286 7.284 7.266 7.263 7.249 7.247 7.033 7.021 7.009 6.732 6.723 1.000 1.991 0.990 1.037 1.059 1.306 1.007 1.001 8.822 8.820 8.801 8.799 8.697 8.685 8.276 8.267 7.633 7.631 7.613 7.612 7.364 7.361 7.346 7.343 7.340 7.325 7.322 7.258 7.255 7.249 7.238 7.237 7.236 7.220 7.218 7.043 7.031 7.019 6.707 6.705 6.698 6.696 0.000 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 2.180 0.845 1.062 1.152 1.345 1.079 1.003 Figure S1. 1 H NMR spectra of the compound 1a and deutrio-1a S-4
10 9 8 7 6 5 4 3 2 1 0 ppm 3.021 1.026 1.066 1.067 1.000 1.026 1.005 2.142 1.076 1.072 3.283 6.685 7.074 7.086 7.098 7.217 7.235 7.255 7.258 7.301 7.321 7.553 7.573 8.601 8.627 8.639 1.225 1.243 1.261 2.881 2.896 2.926 2.941 3.089 3.112 3.134 3.158 3.587 3.605 3.621 3.639 3.657 3.675 3.692 3.708 3.726 4.779 4.794 4.800 4.816 0.000 Figure S2. 1 H NMR spectra of the Compound 3aa S-5
176.057 176.602 157.612 157.736 110.965 115.722 116.769 120.296 122.498 124.063 128.625 133.810 137.239 76.679 76.997 77.315 33.822 36.544 42.263 13.208 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S3. 13 C NMR spectra of the Compound 3aa S-6
8.548 8.571 8.584 8.596 6.611 6.924 6.931 6.947 6.954 7.010 7.016 7.034 7.046 7.058 1.229 1.247 1.265 2.869 2.884 2.914 2.928 3.078 3.102 3.123 3.147 3.592 3.610 3.626 3.643 3.662 3.681 3.697 3.714 3.732 3.860 4.722 4.738-0.000 10 9 8 7 6 5 4 3 2 1 0 ppm 1.117 2.036 1.016 1.022 1.033 1.000 1.030 2.167 3.113 1.057 1.049 3.089 Figure S4. 1 H NMR spectra of the Compound 3ba S-7
176.152 176.682 155.661 157.496 157.662 129.459 132.092 134.238 111.196 113.094 116.486 116.988 102.399 76.677 76.995 77.313 55.599 33.826 36.573 42.547 13.249 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S5. 13 C NMR spectra of the Compound 3ba S-8
10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 2.021 1.007 1.038 1.014 1.019 0.986 2.097 1.027 1.029 3.170 6.618 7.116 7.128 7.140 7.261 7.378 7.383 7.401 7.406 7.681 7.685 8.492 8.514 8.643 8.655 1.221 1.239 1.257 2.878 2.893 2.923 2.938 3.100 3.124 3.145 3.169 3.582 3.600 3.616 3.633 3.651 3.670 3.686 3.703 3.720 4.787 4.802 4.809 4.825-0.000 Figure S6. 1 H NMR spectra of the Compound 3ca S-9
175.825 176.317 157.385 157.829 109.994 115.704 117.117 117.409 122.777 126.805 130.340 135.163 135.959 76.682 76.999 77.317 33.899 36.463 42.209 13.191 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S7. 13 C NMR spectra of the Compound 3ca S-10
10 9 8 7 6 5 4 3 2 1 0 ppm 1.089 2.060 1.000 1.085 1.048 1.086 1.073 2.126 1.063 1.087 3.205 8.624 8.646 8.703 8.715 6.733 7.207 7.219 7.231 7.515 7.537 7.882 2.893 2.908 2.938 2.953 3.135 3.159 3.180 3.204 3.591 3.607 3.624 3.642 3.660 3.676 3.692 4.872 4.893 4.908 1.215 1.232 1.250 0.000 Figure S8. 1 H NMR spectra of the Compound 3da S-11
175.568 176.049 157.198 158.141 105.654 109.900 116.500 117.968 119.909 125.249 126.923 128.493 136.678 138.945 76.749 77.066 77.385 34.015 36.360 41.885 13.169 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S9. 13 C NMR spectra of the Compound 3da S-12
10 9 8 7 6 5 4 3 2 1 0 ppm 1.040 0.991 1.054 2.000 1.226 1.044 1.014 2.152 1.012 1.053 3.216 6.821 7.237 7.249 7.261 7.270 8.154 8.160 8.178 8.183 8.464 8.469 8.618 8.642 8.728 8.740 1.220 1.238 1.255 2.917 2.932 2.962 2.977 3.152 3.175 3.197 3.220 3.579 3.597 3.613 3.630 3.648 3.666 3.682 3.699 3.717 4.894 4.909 4.916 4.931-0.000 Figure S10. 1 H NMR spectra of the Compound 3ea S-13
175.509 175.959 157.157 158.202 137.507 140.186 143.387 110.818 115.810 116.704 118.164 119.150 128.215 76.706 77.023 77.341 34.049 36.306 41.907 13.164 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S11. 13 C NMR spectra of the Compound 3ea S-14
10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 2.079 2.096 2.003 1.017 2.015 0.980 0.993 1.107 2.177 1.079 1.093 3.136 6.863 7.323 7.341 7.359 7.369 7.381 7.394 7.448 7.467 7.486 7.583 7.605 7.702 7.721 7.883 8.532 8.554 8.780 8.792 1.089 1.107 1.124 2.499 2.867 2.883 2.911 2.927 3.082 3.104 3.126 3.149 3.414 3.430 3.448 3.467 3.489 3.507 3.524 3.541 4.950 4.965 4.987 Figure S12. 1 H NMR spectra of the Compound 3fa S-15
175.879 176.655 110.761 115.682 117.887 118.109 122.584 126.739 126.849 128.875 128.918 134.421 135.412 136.047 140.690 156.756 158.535 33.143 35.899 38.891 39.099 39.307 39.516 39.725 39.933 40.142 41.385 12.899 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S13. 13 C NMR spectra of the Compound 3fa S-16
10 9 8 7 6 5 4 3 2 1 0 ppm 2.053 1.000 1.037 1.098 1.064 1.042 1.055 2.135 1.089 1.085 3.274 6.640 7.111 7.123 7.135 7.262 7.333 7.338 7.354 7.358 7.400 7.421 8.646 8.658 8.830 8.831 1.218 1.236 1.254 2.868 2.883 2.913 2.928 3.094 3.117 3.139 3.162 3.577 3.595 3.611 3.628 3.647 3.665 3.681 3.698 3.716 4.781 4.796 4.803 4.818-0.000 Figure S14. 1 H NMR spectra of the Compound 3ga S-17
175.889 176.377 157.395 157.915 110.792 117.204 117.823 118.892 121.378 125.790 127.501 134.648 137.864 76.705 77.022 77.341 33.934 36.506 42.251 13.227 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S15. 13 C NMR spectra of the Compound 3ga S-18
10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 2.084 1.087 1.104 1.086 1.079 1.037 3.061 2.189 1.084 1.092 3.258 9.254 8.688 8.700 6.705 7.136 7.148 7.160 7.571 7.591 7.913 7.934 1.216 1.234 1.253 2.894 2.908 2.938 2.953 3.118 3.141 3.163 3.186 3.576 3.593 3.609 3.626 3.644 3.662 3.678 3.695 3.713 3.945 4.848 4.864 4.870 4.886 0.000 Figure S16. 1 H NMR spectra of the Compound 3ha S-19
175.784 176.224 167.892 157.373 158.080 110.230 117.428 117.741 120.008 123.608 125.693 132.307 136.682 137.313 76.742 77.060 77.378 52.052 33.964 36.503 42.148 13.184 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S17. 13 C NMR spectra of the Compound 3ha S-20
10 9 8 7 6 5 4 3 2 1 0 ppm 2.009 1.000 1.030 1.092 1.060 1.099 1.018 2.080 1.060 1.055 3.127 3.236-0.000 1.234 1.252 1.271 2.363 2.919 2.936 2.964 2.980 3.060 3.083 3.105 3.128 3.576 3.587 3.594 3.611 3.627 3.644 3.661 3.678 3.696 3.711 3.729 3.747 4.597 4.614 4.620 4.637 7.011 7.023 7.035 7.251 7.253 7.261 7.270 7.271 7.317 7.320 7.338 7.341 7.356 7.359 7.542 7.544 7.561 7.563 8.558 8.570 8.650 Figure S18. 1 H NMR spectra of the Compound 3ia S-21
176.560 177.071 157.637 113.674 115.853 116.291 118.568 118.816 122.305 124.501 128.659 130.161 136.390 76.702 77.019 77.336 33.835 36.224 39.794 9.370 13.341 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm Figure S19. 13 C NMR spectra of the Compound 3ia S-22
2.864 2.879 2.909 2.924 3.049 3.072 3.094 3.117 4.643 4.662 4.679 4.702 4.736 4.747 4.782 6.680 6.775 6.787 6.799 7.205 7.224 7.243 7.257 7.287 7.308 7.325 7.332 7.339 7.511 7.518 7.527 7.534 7.555 8.036 8.047 8.630 8.651 0.000 10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 2.014 1.120 4.015 3.168 1.043 1.026 1.002 2.123 1.038 1.049 Figure S20. 1 H NMR spectra of the Compound 4ab S-23
175.844 176.502 112.088 116.080 116.533 120.307 122.567 124.190 128.091 128.698 128.781 129.903 133.165 136.012 137.356 157.475 157.570 76.709 77.027 77.344 36.558 42.737 42.834 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S21. 13 C NMR spectra of the Compound 4ab S-24
10 9 8 7 6 5 4 3 2 1 0 ppm 2.022 1.000 7.094 2.158 1.044 1.031 1.065 1.037 1.131 5.112 5.134 5.150 6.919 7.218 7.236 7.254 7.288 7.307 7.333 7.352 7.373 7.386 7.398 7.421 7.439 7.497 7.516 7.535 7.622 7.641 8.524 8.544 8.814 8.826 2.500 3.048 3.064 3.092 3.108 3.235 3.259 3.280 3.303 Figure S22. 1 H NMR spectra of the Compound 4ac S-25
175.191 176.014 111.092 115.405 117.923 120.314 122.327 123.717 126.682 128.165 128.366 128.974 132.604 134.336 136.608 156.891 158.631 36.063 38.875 39.099 39.297 39.506 39.712 39.931 40.128 41.794 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S23. 13 C NMR spectra of the Compound 4ac S-26
11.243 4.928 4.944 4.950 4.966 6.790 7.190 7.208 7.226 7.259 7.278 7.296 7.398 7.410 7.422 7.585 7.604 8.458 8.479 8.796 8.808 2.501 2.799 2.814 2.843 2.858 3.019 3.042 3.063 3.087 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm 1.010 2.046 1.000 1.013 1.013 0.993 0.998 1.014 0.995 1.008 1.037 Figure S24. 1 H NMR spectra of the Compound 4ad S-27
177.626 178.327 156.827 158.414 110.143 115.107 117.942 120.203 122.139 123.485 128.295 135.113 136.481 37.216 38.889 39.097 39.306 39.515 39.724 39.932 40.142 42.645 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S25. 13 C NMR spectra of the Compound 4ad S-28
10 9 8 7 6 5 4 3 2 1 0 ppm 1.023 2.000 1.026 1.352 1.068 1.007 1.003 1.028 1.083 1.055 1.077 2.089 3.221 2.075 3.296 6.643 7.075 7.085 7.096 7.205 7.223 7.242 7.254 7.285 7.305 7.324 7.542 7.561 8.567 8.587 8.666 8.677-0.000 1.209 1.242 1.282 1.317 1.349 1.380 1.643 1.668 1.827 1.857 2.161 2.190 2.220 2.250 2.856 2.870 2.901 2.915 3.031 3.054 3.075 3.099 4.014 4.044 4.074 4.795 Figure S26. 1 H NMR spectra of the Compound 4ae S-29
176.246 176.759 157.819 157.907 110.576 115.653 116.820 120.335 122.501 124.018 128.714 134.764 137.320 76.724 77.042 77.359 51.845 24.995 25.868 28.875 28.984 36.595 42.009 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S27. 13 C NMR spectra of the Compound 4ae S-30
6.936 7.220 7.238 7.257 7.291 7.311 7.330 7.365 7.377 7.388 7.521 7.542 7.623 7.643 8.080 8.100 8.540 8.560 8.794 8.806 5.122 5.144 5.161 2.499 2.616 3.063 3.080 3.108 3.124 3.257 3.280 3.301 3.347 10 9 8 7 6 5 4 3 2 1 0 ppm 1.000 2.058 2.128 1.074 2.044 1.057 1.152 1.183 1.046 1.022 1.076 1.074 3.117 Figure S28. 1 H NMR spectra of the Compound 4af S-31
197.244 174.853 175.691 111.370 115.468 117.868 120.279 122.294 123.722 126.497 127.032 128.863 134.075 135.999 136.522 136.578 156.814 158.561 26.804 36.037 38.891 39.100 39.308 39.517 39.726 39.934 40.143 41.872 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S29. 13 C NMR spectra of the Compound 4af S-32
6.737 6.883 6.889 6.906 6.912 7.109 7.115 7.140 7.152 7.164 7.342 8.383 8.395 8.431 8.454 2.500 2.839 2.854 2.883 2.898 3.105 3.129 3.150 3.173 3.790 4.570 4.607 4.688 4.724 4.954 4.970 4.976 4.991 10 9 8 7 6 5 4 3 2 1 0 ppm 2.000 1.009 5.187 1.109 1.023 1.048 1.055 1.051 1.046 1.039 3.183 1.021 1.072 Figure S30. 1 H NMR spectra of the Compound 4bb S-33
175.983 176.796 155.175 156.618 158.128 102.369 111.162 112.616 116.531 117.259 127.633 128.319 128.584 129.179 131.285 134.772 136.313 35.883 38.892 39.100 39.309 39.517 39.726 39.935 40.144 41.731 55.310 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S31. 13 C NMR spectra of the Compound 4bb S-34
6.700 6.948 6.954 6.971 6.977 7.011 7.023 7.029 7.035 7.254 7.369 7.387 7.406 7.465 7.483 7.504 8.594 8.606 8.626 8.649 4.784 4.801 4.826 3.021 3.037 3.066 3.082 3.221 3.245 3.267 3.290 3.866-0.000 10 9 8 7 6 5 4 3 2 1 0 ppm 2.000 1.136 2.127 3.052 2.005 1.030 1.073 0.999 3.071 1.015 1.007 Figure S32. 1 H NMR spectra of the Compound 4bc S-35
175.290 175.606 155.822 157.503 157.811 102.558 112.588 113.309 116.472 117.377 125.897 128.267 129.119 129.571 132.254 132.349 133.703 76.710 77.028 77.346 55.670 42.947 36.385 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S33. 13 C NMR spectra of the Compound 4bc S-36
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm 1.024 2.032 1.000 1.017 1.035 1.008 1.013 1.018 3.105 1.090 1.090 11.226 6.708 6.879 6.885 6.902 6.908 7.102 7.108 7.348 7.360 7.372 8.412 8.435 8.747 8.759 2.500 2.777 2.792 2.821 2.836 2.998 3.022 3.043 3.066 3.790 4.873 4.888 4.896 4.911 Figure S34. 1 H NMR spectra of the Compound 4bd S-37
177.634 178.343 155.126 156.709 158.227 129.176 131.211 135.468 110.403 112.468 116.304 117.539 102.328 37.245 38.890 39.099 39.308 39.517 39.725 39.934 40.142 42.923 55.288 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S35. 13 C NMR spectra of the Compound 4bd S-38
2.835 2.850 2.880 2.895 3.028 3.051 3.073 3.096 4.600 4.617 4.638 4.679 4.713 4.722 4.756 6.577 6.768 6.780 6.792 7.250 7.266 7.315 7.324 7.329 7.347 7.351 7.369 7.374 7.492 7.501 7.509 7.638 7.641 8.001 8.011 8.505 8.528-0.000 10 9 8 7 6 5 4 3 2 1 0 ppm 1.033 2.000 4.017 2.062 1.023 1.026 1.003 1.090 2.056 1.048 1.026 Figure S36. 1 H NMR spectra of the Compound 4cb S-39
175.640 176.247 111.254 115.772 116.867 117.766 122.776 126.907 128.149 128.812 129.928 130.373 134.479 135.935 136.022 157.167 157.629 76.746 77.064 77.381 36.449 42.770 42.791 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S37. 13 C NMR spectra of the Compound 4cb S-40
10 9 8 7 6 5 4 3 2 1 0 ppm 2.014 1.000 2.080 3.065 2.067 1.000 1.014 1.008 1.004 1.036 6.912 7.326 7.345 7.400 7.412 7.422 7.438 7.444 7.494 7.513 7.532 7.849 8.460 8.483 8.820 8.832 5.135 5.152 5.157 5.174 2.500 3.060 3.076 3.104 3.120 3.235 3.258 3.279 3.303 3.366 Figure S38. 1 H NMR spectra of the Compound 4cc S-41
175.036 175.763 110.231 114.679 117.318 118.265 122.587 126.100 126.641 128.143 128.933 130.254 132.530 135.338 135.859 156.560 158.694 35.928 38.893 39.101 39.310 39.518 39.727 39.935 40.144 41.699 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S39. 13 C NMR spectra of the Compound 4cc S-42
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm 1.031 2.033 1.000 1.006 2.044 1.015 1.039 1.047 1.078 11.268 6.785 7.392 7.397 7.415 7.419 7.426 7.439 7.451 7.809 7.812 8.394 8.416 8.804 8.816 2.500 2.810 2.825 2.854 2.870 3.017 3.041 3.061 3.085 3.348 4.953 4.969 4.976 4.992 Figure S40. 1 H NMR spectra of the Compound 4cd S-43
177.492 178.081 156.509 158.493 109.124 114.532 117.033 118.287 122.501 125.889 130.210 135.212 136.640 37.117 38.889 39.099 39.307 39.516 39.725 39.934 40.143 42.557 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S41. 13 C NMR spectra of the Compound 4cd S-44
2.949 2.964 2.991 3.006 3.253 3.273 3.294 3.314 3.572 3.684 5.012 5.025 5.040 5.044 5.060 6.637 7.119 7.131 7.143 7.193 7.195 7.213 7.231 7.233 7.258 7.269 7.272 7.290 7.293 7.308 7.311 7.550 7.569 8.459 8.479 8.729 8.741-0.000 10 9 8 7 6 5 4 3 2 1 ppm 2.062 1.008 1.012 1.092 1.114 1.048 1.031 1.002 1.023 3.038 3.000 1.017 Figure S42. 1 H NMR spectra of the Compound 5 S-45
172.171 172.576 157.812 157.912 108.344 114.968 116.938 120.393 122.264 123.685 128.805 136.635 136.898 76.693 77.011 77.328 51.933 52.251 42.220 36.814 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S43. 13 C NMR spectra of the Compound 5 S-46
1.146 1.164 1.182 2.681 2.844 2.858 2.890 2.904 3.113 3.137 3.159 3.183 3.514 3.532 3.542 3.560 4.348 4.362 4.372 4.386 7.181 7.198 7.204 7.246 7.248 7.252 7.255 7.263 7.386 7.391 7.400 7.408 7.415 7.450 7.457 7.458 7.553 7.556 7.558 7.573 7.576 7.578 7.758 7.773 7.777 8.571 8.573 8.575 8.581 8.583 8.585 10 9 8 7 6 5 4 3 2 1 ppm 1.000 1.031 1.016 1.018 2.107 1.388 1.030 0.997 2.109 1.017 1.056 3.191 Figure S44. 1 H NMR spectra of the Compound 7aa S-47
176.523 178.341 159.071 122.136 124.316 127.897 128.755 129.214 130.577 135.790 136.883 140.310 148.779 76.709 77.028 77.345 44.376 33.846 38.716 13.064 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S45. 13 C NMR spectra of the Compound 7aa S-48
1.190 1.208 1.226 2.792 2.807 2.837 2.852 3.181 3.205 3.227 3.250 3.523 3.541 3.557 3.574 3.592 3.609 3.627 3.642 3.660 3.678 4.686 4.701 4.710 4.725 7.180 7.192 7.204 7.217 7.223 7.229 7.232 7.239 7.265 7.428 7.440 7.447 7.451 7.453 7.457 7.463 7.472 7.476 8.165 8.173 8.176 8.182 8.188 8.741 8.753 10 9 8 7 6 5 4 3 2 1 ppm 2.000 1.057 2.049 2.005 1.027 2.150 1.088 1.069 3.193 Figure S46. 1 H NMR spectra of the Compound 7ba S-49
176.590 178.336 165.780 156.878 118.930 128.134 130.419 130.627 131.897 136.251 137.074 76.739 77.058 77.375 45.702 33.794 38.358 13.179 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S47. 13 C NMR spectra of the Compound 7ba S-50
6.250 6.258 6.266 6.285 6.290 6.298 7.019 7.032 7.044 7.274 7.899 7.904 7.907 7.912 8.487 8.499 1.220 1.238 1.256 2.825 2.841 2.870 2.885 3.030 3.053 3.074 3.098 3.599 3.614 3.632 3.650 3.668 3.684 3.686 3.702 3.720 4.561-0.000 O N N O N N 7ca 1 H(CDCl3,400MHz) 10 9 8 7 6 5 4 3 2 1 ppm 2.020 1.000 1.045 2.023 1.008 2.129 1.068 1.057 3.231 Figure S48. 1 H NMR spectra of the Compound 7ca S-51
176.534 177.354 156.360 157.919 122.551 126.918 117.202 110.362 76.734 77.052 77.370 33.745 36.660 41.815 13.276 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S49. 13 C NMR spectra of the Compound 7ca S-52
10 9 8 7 6 5 4 3 2 1 0 ppm 2.026 1.000 2.053 2.065 4.190 2.091 2.112 6.141 1.133 1.144 1.151 1.162 1.169 1.180 2.846 2.861 2.885 2.891 2.899 2.906 2.930 2.944 3.008 3.031 3.043 3.053 3.066 3.076 3.088 3.112 3.496 3.512 3.517 3.521 3.530 3.535 3.540 3.549 3.553 3.558 3.567 3.573 4.670 4.679 4.696 4.711 4.720 4.734 6.199 6.202 7.136 7.141 7.149 7.153 7.161 7.165 7.286 8.551 8.563 Figure S50. 1 H NMR spectra of the Compound 7ca S-53
176.005 176.042 176.714 176.807 156.897 157.059 157.948 158.008 129.674 129.957 118.127 112.549 76.754 77.072 77.390 33.768 36.046 36.552 41.060 41.127 13.070 13.092 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S51. 13 C NMR spectra of the Compound 7ca S-54
1.137 1.155 1.173 1.220 1.237 1.255 2.878 2.892 2.924 2.938 3.009 3.032 3.054 3.078 3.466 3.483 3.499 3.516 3.533 3.550 3.566 3.568 3.583 3.602 4.103 4.120 4.138 4.156 4.701 4.715 4.724 4.738 6.156 6.195 6.618 7.170 7.191 7.210 7.229 7.264 7.285 7.298 7.310 7.407 7.426 7.596 7.615 7.617 8.748 8.760 O N N O N N 8 O OEt 1 H(CDCl3,400MHz) 9 8 7 6 5 4 3 2 1 0 ppm 2.035 2.081 1.026 1.076 1.046 1.066 1.000 1.014 2.041 2.060 1.058 1.098 3.061 3.104 Figure S52. 1 H NMR spectra of the Compound 8 S-55
175.450 175.745 166.733 158.160 158.789 106.294 117.273 119.303 120.922 122.201 122.595 123.549 129.604 135.689 136.460 142.676 76.749 77.067 77.385 60.183 34.006 36.412 39.828 12.991 14.316 O N N O N N 8 O OEt 13 C(CDCl3,100MHz) 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm Figure S53. 13 C NMR spectra of the Compound 8 S-56