Supporting Information for

Supporting Information for Acceptorless Dehydrogenation of N-Heterocycles and Secondary Alcohols by Ru(II)-NNC Complexes Bearing a Pyrazoyl-Indolyl-Pyridine Ligand Qingfu Wang,, Huining Chai,, and Zhengkun Yu*,, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, People s Republic of China; University of Chinese Academy of Sciences, Beijing 100049, People s Republic of China; State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, People s Republic of China. zkyu@dicp.ac.cn Contents: 1. General considerations S2 2. X-Ray crystallographic studies S3 3. Analytical data S4 4. Copies of NMR spectra S16 S1

1. General considerations The spectroscopic features of known compounds 7a-7e, 1 7f, 2 7g, 3 7h, 1 7i-7j, 4 7k-7l, 1 7m, 5 7n, 6 7o, 3 7p-7q, 1 7r, 7 9a-9d, 1 9e, 8 9f-9j, 9 9k-9l, 10 9m, 11 9n, 12 11a-11b, 1 12a-12b, 1 14a, 13 14b, 14 14c, 15 14d-14j, 13 14k, 16 14l, 14 14m, 17 14n-14o, 18 14p, 17 14q, 19 and 14r 20 are in good agreement with those reported in the literatures. References (1) Wu, J.; Talwar, D.; Johnston, S.; Yan, M.; Xiao, J. Angew. Chem., Int. Ed. 2013, 52, 6983-6987. (2) El-Damasy, A. K.; Seo, S. H.; Cho. N.-C.; Kang, S. B.; Pae, A. N.; Kim, K.-S.; Keum, G. J. Med. Chem. 2015, 101, 754-758. (3) Mullick, K.; Biswas, S.; Angeles-Boza, A. M.; Suib, S. L. Chem. Commun. 2017, 53, 2256-2259. (4) Kojima, M.; Kanai, M. Angew. Chem., Int. Ed. 2016, 55, 12224-12227. (5) Brown, W. D.; Gouliaev, A. H. Synthesis 2002, 1, 83-86. (6) Muthaiah, S.; Hong, S. H. Adv. Synth. Catal. 2012, 354, 3045-3053. (7) Ucar, S.; Essiz, S.; Dastan, A. Tetrahedron 2017, 73,1618-1632. (8) Wang, X.-W.; Hua, Y.-Z.; Wang, M.-C. J. Org. Chem. 2016, 81, 9227-9234. (9) He, K. H.; Tan, F. F.; Zhou, C. Z.; Zhou, G. J.; Yang, X. L.; Li, Y. Angew. Chem., Int. Chem. 2017, 56, 3080-3084. (10) Zhang, J.; Chen, S.; Chen, F.; Xu, W.;Deng, G.-J.; Gong, H. Adv. Synth. Catal. 2012, 359, 2358-2363. (11) Du, P.; Brosmer, J. L.; Peters, D. G. Org. Lett. 2011, 13, 4072-4075. (12) Rodriguez-Dafonte, P.; Terrier, F.; Lakhdar, S.; Kurbatov, S.; Goumont, R. J. Org. Chem. 2009, 74, 3305-3315. (13) Song, H.; Kang, B.; Hong, S. H. ACS Catal. 2014, 4, 2889-2895. (14) Nelson, D. J.; Fernandez-Salas, J. A.; Truscott, B. J.; Nolan, S. P. Org. Biomol. Chem. 2014, 12, 6672-6676. (15) Nobuta, T.; Hirashima, S.; Tada, N.; Miura, T.; Itoh, A. Org. Lett. 2011, 13, 2576-2579. (16) Zhou, X.; Li, X.; Zhang, W.; Chen, J. Tetrahedron Lett. 2014, 55, 5137-5140. (17) Baratta, W.; Bossi, G.; Putignano, E.; Rigo, P. Chem.-Eur. J. 2011, 17, 3474-3481. S2

(18) Kawahara, R.; Fujita, K.; Yamaguchi, R. Angew. Chem., Int. Chem. 2012, 51, 12790-12794. (19) Mo, F.; Lim, H. N.; Dong, G. J. Am. Chem. Soc. 2015, 137, 15518-15527. (20) Li, X.; Wang, Y.; Gao, Y.; Li, L.; Guo, X.; Liu, D.; Jing, Y.; Zhao, L. Org. Biomol. Chem. 2014, 12, 6706-6716. 2. X-Ray crystallographic studies Figure S1. Molecular structure of 5b. Figure S1. Molecular structure of 5b. Table S1. Crystal data and structure refinement for 5b. Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = 22.9293(7) Å α= 90. b = 11.1509(4) Å β= 105.166(3). c = 19.7810(6) Å γ = 90. Volume 4881.5(3) Å 3 Z 4 Density (calculated) 1.284 Mg/m 3 Absorption coefficient 0.429 mm -1 F(000) 1952 Crystal size 0.200 x 0.160 x 0.130 mm 3 Theta range for data collection 2.982 to 26.000. Index ranges Reflections collected 28901-28<=h<=28, -13<=k<=12, -24<=l<=24 S3

Independent reflections 9565 [R(int) = 0.0295] Completeness to theta = 25.242 99.8 % Absorption correction 3. Analytical data Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.8348 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 9565 / 1 / 575 Goodness-of-fit on F 2 1.060 Final R indices [I>2sigma(I)] R1 = 0.0366, wr2 = 0.0907 R indices (all data) R1 = 0.0508, wr2 = 0.0966 Extinction coefficient n/a Largest diff. peak and hole 0.326 and -0.274 e.å -3 Quinoline (7a): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.89-8.83 (m, 1 H), 8.12-8.01 (m, 2 H), 7.73 (dd, J = 8.9, 4.8 Hz, 1 H), 7.68-7.61 (m, 1 H), 7.52-7.43 (m, 1H), 7.30 (td, J = 8.2, 4.5 Hz, 1H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 150.3, 148.2, 136.0, 129.4, 129.4, 128.2, 127.8, 126.5, 121.0. 2-Methylquinoline (7b): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.99 (d, J = 8.5 Hz, 1 H), 7.93 (d, J = 8.3 Hz, 1 H), 7.68 (d, J = 8.0 Hz, 1 H), 7.65-7.58 (m, 1 H), 7.40 (dd, J = 7.8, 7.1 Hz, 1 H), 7.18 (d, J = 8.4 Hz, 1 H), 2.68 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 158.9, 147.8, 136.1, 129.4, 128.6, 127.5, 126.4, 125.6, 121.9, 25.3. N Ph 2-Phenylquinoline (7c): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.08-7.98 (m, 3 H), 7.94 (d, J = 8.6 Hz, 1 H), 7.67-7.50 (m, 3 H), 7.40-7.28 (m, 4 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 157.3, 148.3, 139.7, 136.7, 129.7, 129.6, 129.3, 128.8, 127.6, 127.5, 127.2, 126.3, 118.9. S4

3-Methylquinoline (7d): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.65-8.60 (m, 1 H), 8.03-7.95 (m, 1 H), 7.70-7.61 (m, 1 H), 7.59-7.44 (m, 2 H), 7.39-7.29 (m, 1 H), 2.30 (m, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 152.1, 146.2, 134.4, 130.2, 128.8, 128.20, 127.9, 126.9, 126.3, 18.4. 4-Methylquinoline (7e): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.83-8.70 (m, 1 H), 8.10 (d, J = 8.4 Hz, 1 H), 7.97 (dd, J = 7.1, 3.9 Hz, 1 H), 7.69 (td, J = 6.9, 1.6 Hz, 1 H), 7.60-7.49 (m, 1 H), 7.20 (s, 1 H), 2.68 (d, J = 3.8 Hz, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 150.2, 148.1, 144.4, 130.1, 129.2, 128.38, 126.4, 123.9, 121.9, 18.7. 5-Methoxyquinoline (7f): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.84 (d, J = 2.4 Hz, 1 H), 8.49 (d, J = 8.3 Hz, 1 H), 7.67 (d, J = 8.6 Hz, 1 H), 7.53 (t, J = 8.1 Hz, 1 H), 7.28 (dd, J = 8.4, 4.2 Hz, 1 H), 6.74 (d, J = 7.6 Hz, 1 H), 3.88 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 155.0, 150.5, 148.9, 130.7, 129.3, 121.3, 120.7, 120.0, 104.1, 55.6. 6-Methoxyquinoline (7g): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.68 (m, 1 H), 7.94 (m, 2 H), 7.35-7.18 (m, 2 H), 6.93 (m, 1 H), 3.80 (m, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 157.57, 147.7, 144.2, 134.7, 130.6, 129.2, 122.2, 121.2, 105.0, 55.4. 6-Fluoro-2-methylquinoline (7h): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.96-7.86 (m, 1 H), 7.85-7.73 (m, 1 H), 7.39-7.27 (m, 1H), 7.27-7.17 (m, 1 H), 7.17-7.07 (m, 1 H), 2.69-2.55 (m, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 161.0 (d, J = 294.0 Hz), 158.5, 144.7, 135.2, 130.9 (d, J = 9.0 Hz), 126.8 (d, J = 13.4 Hz), 122.5, 119.3 (d, J = 25.2 Hz), 110.4 (d, J = 21.2 Hz), 25.0. S5

8-Methylquinoline (7i): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.99-8.91 (m, 1 H), 8.12-8.02 (m, 1 H), 7.61 (d, J = 7.5 Hz, 1 H), 7.54 (s, 1 H), 7.45-7.30 (m, 2 H), 2.84 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 149.2, 147.3, 137.0, 136.3, 129.6, 128.2, 126.3, 125.9, 120.8, 18.2. Benzo[h]quinoline (7j): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 9.35 (d, J = 8.1 Hz, 1 H), 9.01 (dd, J = 4.3, 1.5 Hz, 1 H), 8.16-8.07 (m, 1 H), 7.90 (d, J = 7.8 Hz, 1H), 7.81-7.74 (m, 2 H), 7.73-7.67 (m, 1 H), 7.63 (d, J = 8.8 Hz, 1 H), 7.48 (dd, J = 7.9, 4.3 Hz, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 148.8, 146.6, 135.8, 133.7, 131.55, 128.2, 127.9, 127.8, 127.1, 126.4, 125.4, 124.4, 121.8. Isoquinoline (7k): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 9.00 (s, 1 H), 8.30 (d, J = 5.8 Hz, 1 H), 7.60 (d, J = 8.2 Hz, 1 H), 7.46 (d, J = 8.2 Hz, 1 H), 7.38-7.32 (m, 1 H), 7.30 (d, J = 5.8 Hz, 1 H), 7.28-7.23 (m, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 152.0, 142.5, 135.2, 129.8, 128.1, 127.0, 126.7, 125.9, 119.9. 1-Phenylisoquinoline (7l): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.62 (d, J = 5.6 Hz, 1 H), 8.11 (d, J = 8.5 Hz, 1 H), 7.88 (d, J = 8.2 Hz, 1 H), 7.74-7.62 (m, 4 H), 7.58-7.47 (m, 4 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 160.8, 142.3, 139.6, 137.0, 130.1, 130.0, 128.7, 128.5, 127.7, 127.3, 127.1, 126.8, 120.0. 5-Bromoisoquinoline (7m): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 9.60-9.44 (m, 1 H), 8.59-8.48 (m, 1 H), 7.84-7.59 (m, 2 H), 7.59-7.33 (m, 2 S6

H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 151.8, 143.8, 137.1, 131.2, 130.6, 126.7, 126.4, 122.4, 120.0. Isoquinoline (7n): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.72 (dd, J = 4.2, 1.6 Hz, 1 H), 8.21 (d, J = 8.2 Hz, 1 H), 7.92 (d, J = 9.2 Hz, 1 H), 7.43 (dd, J = 8.3, 4.2 Hz, 1 H), 7.38 (dd, J = 9.2, 2.8 Hz, 1 H), 7.31 (d, J = 2.8 Hz, 1 H), 3.86 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 157.3, 147.9, 143.9, 134.8, 130.4, 129.1, 122.1, 121.7, 105.7, 55.5. Quinoxaline (7o): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.68 (s, 2 H), 7.95 (dd, J = 6.4, 3.5 Hz, 2 H), 7.59 (dd, J = 6.4, 3.4 Hz, 2 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 144.8, 142.8, 129.8, 129.3. 2-Methylquinoxaline (7p): yellow liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.65 (s, 1 H), 8.00 (d, J = 7.9 Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7.63 (dd, J = 9.0, 7.4 Hz, 2 H), 2.69 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 153.7, 145.9, 142.0, 140.9, 129.9, 129.1, 128.8, 128.6, 22.5. 5-Methylquinoxaline (7q): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.75 (m, 2 H), 7.86 (d, J = 7.1 Hz, 1 H), 7.60-7.46 (m, 2 H), 2.71 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 144.5, 143.6, 143.1, 142.1, 137.6, 130.0, 129.7, 127.3, 77.5, 77.2, 76.8, 17.2. 6-Bromoquinoxaline (7r): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.79 (d, J = 1.8 Hz, 2 H), 8.23 (d, J = 2.0 Hz, 1 H), 7.91 (d, J = 8.9 Hz, 1 H), 7.78 (dd, J = 8.9, 2.0 Hz, 1 H), 7.26 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 145.7, 145.2, 143.5, 141.8, 133.7, 131.8, 130.9, 124.1. S7

Indole (9a): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.98 (s, 1 H), 7.81 (d, J = 7.5 Hz, 1 H), 7.44 (d, J = 8.1 Hz, 1 H), 7.38-7.33 (m, 1 H), 7.32-7.26 (m, 1 H), 7.24-7.19 (m, 1 H), 6.73-6.63 (m, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 135.8, 127.9, 124.3, 122.0, 120.8, 119.9, 111.2, 102.5. 2-Methyl-1H-indole (9b): yellow solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.72 (s, 1 H), 7.63-7.54 (m, 1 H), 7.28 (d, J = 7.5 Hz, 1 H), 7.22-7.10 (m, 2 H), 6.27 (s, 1 H), 2.43 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 136.1, 135.2, 129.1, 121.0, 119.7, 110.4, 100.4, 77.5, 77.1, 76.8, 13.7. 2-Phenyl -1H-indole (9c): white solid. 1 H NMR (DMSO-d 6, 400 MHz, 23 C) δ 11.55 (s, 1 H), 7.87 (d, J = 7.6 Hz, 2 H), 7.54 (d, J = 7.8 Hz, 1 H), 7.45 (dd, J = 14.3, 7.4 Hz, 3 H), 7.31 (t, J = 7.3 Hz, 1 H), 7.11 (t, J = 7.4 Hz, 1 H), 7.01 (t, J = 7.4 Hz, 1 H), 6.90 (d, J = 1.3 Hz, 1 H). 13 C{ 1 H} NMR (DMSO-d 6, 100 MHz, 23 C) δ 137.7, 137.2, 132.3, 129.0, 128.7, 127.4, 125.0, 121.6, 120.1, 119.4, 111.4, 98.7. 3-Methyl-1H-indole (9d): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.85 (s, 1 H), 7.67 (d, J = 7.8 Hz, 1 H), 7.40 (d, J = 8.0 Hz, 1 H), 7.30-7.25 (m, 1 H), 7.24-7.18 (m, 1 H), 7.01 (s, 1 H), 2.42 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 136.4, 128.4, 122.0, 121.7, 119.2, 118.9, 111.8, 111.1, 9.8. 4-Methoxy-1H-indole (9e): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.13 (s, 1 H), 7.30 (t, J = 7.8 Hz, 1 H), 7.09 (d, J = 8.5 Hz, 2 H), 6.85 (s, 1 H), 6.71 (d, J = 7.6 Hz, 1 H), 4.10 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 153.3, 137.2, 122.9, 122.7, 118.5, 104.7, 99.6, 99.6, 55.3. S8

5-Methoxy-1H-indole (9f): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.11 (s, 1 H), 7.31 (d, J = 8.9 Hz, 1 H), 7.24-7.17 (m, 2 H), 6.97 (dd, J = 8.8, 2.2 Hz, 1 H), 6.57 (s, 1 H), 3.95 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 154.2, 131.1, 128.3, 125.1, 112.4, 111.9, 102.4, 102.3, 56.0. 7-Methyl-1H-indole (9g): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.04 (s, 1 H), 7.55 (d, J = 7.7 Hz, 1 H), 7.21 (t, J = 2.8 Hz, 1 H), 7.14-7.01 (m, 2 H), 6.60 (t, J = 2.3 Hz, 1 H), 2.52 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 135.5, 127.5, 123.9, 122.6, 120.3, 120.1, 118.6, 103.2, 16.8. 5-Fluoro-1H-indole (9h): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.08 (s, 1 H), 7.47 (d, J = 9.5 Hz, 1 H), 7.34 (dd, J = 8.4, 4.1 Hz, 1 H), 7.27 (s, 1 H), 7.16-7.06 (m, 1 H), 6.66 (s, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 159.2 (d, J = 232.2 Hz), 132.4, 128.2 (d, J = 10.2 Hz), 126.2, 111.8 (d, J = 9.7 Hz), 110.5 (d, J = 26.2 Hz), 105.5 (d, J = 23.2 Hz), 102.7 (d, J = 4.7 Hz). 5-Chloro-1H-indole (9i): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.12 (s, 1 H), 7.71 (s, 1 H), 7.32 (d, J = 8.7 Hz, 1 H), 7.24 (d, J = 2.8 Hz, 2 H), 6.57 (s, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 134.2, 129.0, 125.7, 125.4, 122.3, 120.1, 112.2, 102.4. 5-Bromo-1H-indole (9j): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.08 (s, 1 H), 7.82 (s, 1 H), 7.32 and 7.23 (d each, J = 8.6 Hz, 1:1 H), 7.18 (s, 1 H), 6.53 (s, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 134.4, 129.7, 125.6, 124.8, 123.2, 113.0, 112.6, 102.3. S9

5-Nitro-1H-indole (9k): yellow solid. 1 H NMR (CD 3 OD, 400 MHz, 23 C) δ 8.49 (s, 1 H), 7.98 (d, J = 8.7 Hz, 1 H), 7.42 (m, 2 H), 6.63 (s, 1 H). 13 C{ 1 H} NMR (CD 3 OD, 100 MHz, 23 C) δ 142.5, 140.6, 129.3, 128.6, 118.3, 117.6, 112.2, 104.9. 6-Chloro-1H-indole (9l): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.08 (s, 1 H), 7.57 (d, J = 8.4 Hz, 1 H), 7.37 (s, 1 H), 7.18 (t, J = 2.4 Hz, 1 H), 7.13 (d, J = 8.4 Hz, 1 H), 6.56 (s, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 136.2, 127.9, 126.5, 125.0, 121.7, 120.7, 111.1, 102.9. 5,6-Methylenedioxy-2-phenylindole (9m): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.24 (s, 1 H), 7.62 (d, J = 7.6 Hz, 2 H), 7.45 (t, J = 7.5 Hz, 2 H), 7.31 (d, J = 7.7 Hz, 1 H), 7.04 (s, 1 H), 6.90 (s, 1 H), 6.75 (s, 1 H), 5.98 (s, 2 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 145.3, 143.4, 132.6, 132.0, 129.1, 127.3, 124.7, 123.4, 100.8, 100.4, 99.3, 92.0. 5-Chloro-2-methyl-1H-indole (9n): yellow solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.81 (s, 1 H), 7.49 (s, 1 H), 7.16 (d, J = 8.5 Hz, 1 H), 7.07 (d, J = 8.5 Hz, 1 H), 6.17 (s, 1 H), 2.42 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 136.8, 134.5, 130.3, 125.3, 121.2, 119.1, 111.2, 100.3, 13.8. 1-Methyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole (11a): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.14 (s, 1 H), 7.50 (d, J = 7.5 Hz, 1 H), 7.30 (d, J = 7.8 Hz, 1 H), 7.14 (dt, J = 14.7, 7.0 Hz, 2 H), 4.17 (q, J = 6.5 Hz, 1 H), 3.37 (dt, J = 12.8, 4.5 Hz, 1 H), 3.11-3.00 (m, 1 H), 2.85-2.67 (m, 2 H), 2.35 (d, J = 5.9 Hz, 1 H), S10

1.45 (d, J = 6.7 Hz, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 137.0, 135.8, 127.6, 121.6, 119.4, 118.2, 110.9, 108.4, 48.3, 42.7, 22.7, 20.7. 1-Phenyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole (11b): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.01 (s, 1 H), 7.59 (dd, J = 5.6, 2.9 Hz, 1 H), 7.37 (dd, J = 6.5, 3.5 Hz, 3 H), 7.32-7.26 (m, 2 H), 7.21-7.13 (m, 3 H), 5.12 (s, 1 H), 3.34 (dt, J = 9.1, 4.8 Hz, 1 H), 3.18-3.07 (m, 1 H), 3.01-2.90 (m, 1 H), 2.89-2.80 (m, 1 H), 1.97 (s, 1 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 141.8, 136.0, 134.5, 128.9, 128.6, 128.3, 127.4, 121.7, 119.4, 118.3, 110.9, 110.2, 58.1, 42.8, 22.5. 1-Methyl-9H-pyrido[3,4-b]indole (12a): white solid. 1 H NMR (DMSO-d 6, 400 MHz, 23 C) δ 11.58 (s, 1 H), 8.18 (d, J = 6.8 Hz, 2 H), 7.91 (d, J = 3.3 Hz, 1 H), 7.60 (d, J = 7.6 Hz, 1 H), 7.52 (t, J = 7.1 Hz, 1 H), 7.22 (t, J = 6.7 Hz, 1 H), 2.76 (s, 3 H). 13 C{ 1 H} NMR (DMSO-d 6, 100 MHz, 23 C) δ 142.2, 140.4, 137.6, 134.6, 127.9, 127.0, 121.8, 121.1, 119.3, 112.7, 112.0, 20.5. 1-Phenyl-9H-pyrido[3,4-b]indole (12b): white solid. 1 H NMR (DMSO-d 6, 400 MHz, 23 C) δ 11.54 (s, 1 H), 8.46 (d, J = 5.1 Hz, 1 H), 8.25 (d, J = 7.8 Hz, 1 H), 8.11 (d, J = 5.1 Hz, 1 H), 8.04 (d, J = 7.8 Hz, 2 H), 7.67 (d, J = 8.2 Hz, 1 H), 7.61 (t, J = 7.5 Hz, 2 H), 7.53 (dt, J = 14.5, 7.3 Hz, 2 H), 7.26 (t, J = 7.5 Hz, 1 H). 13 C{ 1 H} NMR (DMSO-d 6, 100 MHz, 23 C) δ 142.2, 141.2, 138.4, 133.1, 129.3, 128.8, 128.6, 128.4, 128.2, 121.6, 120.9, 119.6, 113.9, 112.5. Acetophenone (14a): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.95 (d, J = 7.5 Hz, 2 H), 7.56 (t, J = 7.3 Hz, 1 H), 7.45 (t, J = 7.7 Hz, 2 H), 2.60 (s, 3 S11

H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 198.2, 137.2, 133.2, 128.7, 128.4, 26.7. Propiophenone (14b): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.01-7.92 (m, 2 H), 7.60-7.50 (m, 1 H), 7.44 (dd, J = 10.5, 4.6 Hz, 2 H), 3.00 (q, J = 7.2 Hz, 2 H), 1.22 (t, J = 7.2 Hz, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 200.9, 137.0, 133.0, 128.6, 128.1, 31.9, 8.3. 2'-Methylacetophenone (14c): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.72 (d, J = 7.6 Hz, 1 H), 7.40 (t, J = 7.5 Hz, 1 H), 7.28 (dd, J = 11.8, 7.6 Hz, 2 H), 2.60 (s, 3 H), 2.56 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 201.8, 138.5, 137.7, 132.1, 131.6, 129.4, 125.8, 29.6, 21.7. 3'-Methylacetophenone (14d): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) 7.73 (m, 2 H), 7.31 (m, 2 H), 2.54 (s, 3 H), 2.37 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 198.1, 138.2, 137.0, 133.7, 128.6, 128.3, 125.4, 26.5, 21.1. 4'-Methylacetophenone (14e): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.89 (d, J = 8.2 Hz, 2 H), 7.29 (d, J = 8.0 Hz, 2 H), 2.61 (s, 3 H), 2.44 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 198.1, 144.0, 134.9, 129.4, 128.6, 26.6, 21.7. 4'-Methoxyacetophenone (14f): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.88 (d, J = 8.9 Hz, 2 H), 6.88 (d, J = 8.9 Hz, 2 H), 3.81 (s, 3 H), 2.50 (s, 3 S12

H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 196.7, 163.5, 130.6, 130.3, 113.7, 55.4, 26.3. 4'-Chloroacetophenone (14g): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.96-7.80 (m, 2 H), 7.49-7.35 (m, 2 H), 2.58 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 196.9, 139.7, 135.6, 129.9, 129.0, 26.7. 4'-Trifluoromethylacetophenone (14h): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.0 (d, J = 8.1 Hz, 2 H), 7.7 (d, J = 8.2 Hz, 2 H), 2.6 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 197.0, 139.8, 134.2 (q, J = 32.5 Hz), 128.7, 125.7 (q, J = 3.7 Hz), 122.3 (q, J = 270.9 Hz), 26.7. Acetophenone (14i): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 8.44 (s, 1 H), 8.02 (d, J = 8.6 Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7.86 (dd, J = 8.3, 3.7 Hz, 2 H), 7.56 (dt, J = 14.9, 6.9 Hz, 2 H), 2.70 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 198.1, 135.6, 134.5, 132.6, 130.2, 129.6, 128.5, 128.4, 127.8, 126.8, 123.9, 26.7. Benzophenone (14j): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.85-7.78 (m, 4 H), 7.59 (dd, J = 10.6, 4.2 Hz, 2 H), 7.48 (t, J = 7.6 Hz, 4 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 196.8, 137.7, 132.5, 130.2, 128.4. 1,5-Diphenylpentan-3-one (14k): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.42-7.17 (m, 10 H), 2.94 (t, J = 7.5 Hz, 4 H), 2.76 (t, J = 7.5 Hz, 4 H). S13

13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 209.2, 141.1, 128.6, 128.4, 126.2, 44.6, 29.9. 4-Phenylbutan-2-one (14l): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 7.33 (t, J = 7.2 Hz, 2 H), 7.24 (t, J = 6.6 Hz, 3 H), 2.94 (t, J = 7.5 Hz, 2 H), 2.80 (t, J = 7.6 Hz, 2 H), 2.18 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 207.9, 141.0, 128.5, 128.3, 126.1, 45.2, 30.1, 29.8. O 4 Heptan-2-one (14m): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 2.40 (t, J = 7.5 Hz, 2 H), 2.12 (s, 3 H), 1.62-1.51 (m, 2 H), 1.37-1.21 (m, 4 H), 0.88 (t, J = 7.0 Hz, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 209.5, 43.9, 31.5, 30.0, 23.7, 22.6, 14.0. O 5 Octan-2-one (14n): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 2.41 (t, J = 7.5 Hz, 2 H), 2.12 (s, 3 H), 1.61-1.50 (m, 2 H), 1.28 (m, 6 H), 0.87 (t, J = 6.7 Hz, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 209.6, 44.0, 31.7, 30.0, 29.0, 24.0, 22.6, 14.1. Cyclohexanone (14o): colorless liquid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 2.31 (t, J = 6.7 Hz, 4 H), 1.91-1.76 (m, 4 H), 1.72-1.66 (m, 2 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 212.4, 42.0, 27.1, 25.1. Cholest-4-en-3-one (14p): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ1h NMR (400 MHz, CDCl3) δ 5.72 (s, 1 H), 2.50-2.33 (m, 4 H), 2.05-1.99 (m, 2 H), 1.84 S14

(m, 2 H), 1.56-1.49 (m, 4 H), 1.35 (m, 4 H), 1.15 (m, 12 H), 1.01 (m, 2 H), 0.93 (m, 10 H), 0.70 (m, 4 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) 199.8, 171.9, 123.9, 56.2, 56.0, 53.9, 42.5, 39.7, 39.6, 38.7, 36.2, 35.9, 35.8, 35.7, 34.1, 33.1, 32.2, 28.3, 28.1, 24.3, 23.9, 23.0, 22.7, 21.1, 18.8, 17.5, 12.1. Dihydrocholesterone (14q): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 2.42-2.31 (m, 1 H), 2.30-2.17 (m, 2 H), 2.10-1.94 (m, 3 H), 1.86-1.74 (m, 1 H), 1.72-1.64 (m, 1 H), 1.58-1.44 (s, 4 H), 1.43-1.26 (m, 8 H), 1.24-0.94 (m, 12 H), 0.93-0.80 (dd, J = 6.5, 1.2 Hz, 10 H), 0.75-0.68 (m, 1 H), 0.66 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 212.1, 56.4, 53.9, 46.8, 44.8, 42.7, 40.0, 39.6, 38.7, 38.3, 36.3, 35.9, 35.7, 35.5, 31.8, 29.1, 28.3, 28.1, 24.3, 23.9, 22.9, 22.7, 21.6, 18.8, 12.2, 11.6. (18β,20β)-3,11-Dioxoolean-12-en-29-oic acid methyl ester (14r): white solid. 1 H NMR (CDCl 3, 400 MHz, 23 C) δ 5.68 (s, 1 H), 3.67 (s, 3 H), 2.95 (m, 1 H), 2.61 (m, 1 H), 2.42 (s, 1 H), 2.34 (m, 1 H), 2.13-1.94 (m, 3 H), 1.94-1.77 (m, 2 H), 1.74-1.48 (m, 5 H), 1.47-1.23 (m, 13 H), 1.15 (t, J = 7.3 Hz, 6 H), 1.07 (d, J = 14.3 Hz, 6 H), 0.80 (s, 3 H). 13 C{ 1 H} NMR (CDCl 3, 100 MHz, 23 C) δ 217.2, 199.5, 177.0, 169.8, 128.6, 61.2, 55.5, 51.9, 48.5, 47.9, 45.3, 44.1, 43.4, 41.3, 39.9, 37.9, 36.8, 34.3, 26.5, 23.4, 21.5, 18.9, 18.6. S15

4. Copies of NMR spectra Figure S2. 1 H NMR spectrum of 3a (CDCl 3, 400 MHz, 23 o C). Figure S3. 13 C{ 1 H} NMR spectrum of 3a (CDCl 3, 100 MHz, 23 o C). S16

Figure S4. 1 H NMR spectrum of 3b (CDCl 3, 400 MHz, 23 o C). Figure S5. 13 C{ 1 H} NMR spectrum of 3b (CDCl 3, 100 MHz, 23 o C). S17

Figure S6. 1 H NMR spectrum of 3c (CDCl 3, 400 MHz, 23 o C). Figure S7. 13 C{ 1 H} NMR spectrum of 3c (CDCl 3, 100 MHz, 23 o C). S18

Figure S8. 1 H NMR spectrum of 4a (CDCl 3, 400 MHz, 23 o C). Figure S9. 13 C{ 1 H} NMR spectrum of 4a (CDCl 3, 100 MHz, 23 o C). S19

Figure S10. 31 P NMR spectrum of complex 4a (CDCl 3, 162 MHz, 23 o C). Figure S11. 1 H NMR spectrum of 4b (CDCl 3, 400 MHz, 23 o C). S20

Figure S12. 13 C{ 1 H} NMR spectrum of 4b (CDCl 3, 100 MHz, 23 o C). Figure S13. 31 P NMR spectrum of complex 4b (CDCl 3, 162 MHz, 23 o C). S21

Figure S14. 1 H NMR spectrum of 4c (CDCl 3, 400 MHz, 23 o C). Figure S15. 31 P NMR spectrum of complex 4c (CDCl 3, 162 MHz, 23 o C). S22

Figure S16. 1 H NMR spectrum of 5a (C 6 D 6- d 6, 400 MHz, 23 o C). Figure S17. 13 C{ 1 H} NMR spectrum of 5a (C 6 D 6- d 6, 100 MHz, 23 o C). S23

Figure S18. 31 P{ 1 H} NMR spectrum of 5a (C 6 D 6- d 6, 162 MHz, 23 o C). Figure S19. 1 H NMR spectrum of 5b (C 6 D 6- d 6, 400 MHz, 23 o C). S24

Figure S20. 13 C{ 1 H} NMR spectrum of 5b (C 6 D 6- d 6, 100 MHz, 23 o C). Figure S21. 31 P{ 1 H} NMR spectrum of 5b (C 6 D 6- d 6, 162 MHz, 23 o C). S25

Figure S22. 1 H NMR spectrum of 7a (CDCl 3, 400 MHz, 23 o C). Figure S23. 13 C{ 1 H} NMR spectrum of 7a (CDCl 3, 100 MHz, 23 o C). S26

Figure S24. 1 H NMR spectrum of 7b (CDCl 3, 400 MHz, 23 o C). Figure S25. 13 C{ 1 H} NMR spectrum of 7b (CDCl 3, 100 MHz, 23 o C). S27

Figure S26. 1 H NMR spectrum of 7c (CDCl 3, 100 MHz, 23 o C). Figure S27. 13 C{ 1 H} NMR spectrum of 7c (CDCl 3, 100 MHz, 23 o C). S28

Figure S28. 1 H NMR spectrum of 7d (CDCl 3, 400 MHz, 23 o C). Figure S29. 13 C{ 1 H} NMR spectrum of 7d (CDCl 3, 100 MHz, 23 o C). S29

Figure S30. 1 H NMR spectrum of 7e (CDCl 3, 400 MHz, 23 o C). Figure S31. 13 C{ 1 H} NMR spectrum of 7e (CDCl 3, 100 MHz, 23 o C). S30

Figure S32. 1 H NMR spectrum of 7f (CDCl 3, 400 MHz, 23 o C). Figure S33. 13 C{ 1 H} NMR spectrum of 7f (CDCl 3, 100 MHz, 23 o C). S31

Figure S34. 1 H NMR spectrum of 7g (CDCl 3, 400 MHz, 23 o C). Figure S35. 13 C{ 1 H} NMR spectrum of 7g (CDCl 3, 100 MHz, 23 o C). S32

Figure S36. 1 H NMR spectrum of 7h (CDCl 3, 400 MHz, 23 o C). Figure S37. 13 C{ 1 H} NMR spectrum of 7h (CDCl 3, 100 MHz, 23 o C). S33

Figure S38. 1 H NMR spectrum of 7i (CDCl 3, 400 MHz, 23 o C). Figure S39. 13 C{ 1 H} NMR spectrum of 7i (CDCl 3, 100 MHz, 23 o C). S34

Figure S40. 1 H NMR spectrum of 7j (CDCl 3, 400 MHz, 23 o C). Figure S41. 13 C{ 1 H} NMR spectrum of 7j (CDCl 3, 100 MHz, 23 o C). S35

Figure S42. 1 H NMR spectrum of 7k (CDCl 3, 400 MHz, 23 o C). Figure S43. 13 C{ 1 H} NMR spectrum of 7k (CDCl 3, 100 MHz, 23 o C). S36

Figure S44. 1 H NMR spectrum of 7l (CDCl 3, 400 MHz, 23 o C). Figure S45. 13 C{ 1 H} NMR spectrum of 7l (CDCl 3, 100 MHz, 23 o C). S37

Figure S46. 1 H NMR spectrum of 7m (CDCl 3, 400 MHz, 23 o C). Figure S47. 13 C{ 1 H} NMR spectrum of 7m (CDCl 3, 100 MHz, 23 o C). S38

Figure S48. 1 H NMR spectrum of 7n (DMSO-d 6, 400 MHz, 23 o C). Figure S49. 13 C{ 1 H} NMR spectrum of 7n (DMSO-d 6, 100 MHz, 23 o C). S39

Figure S50. 1 H NMR spectrum of 7o (CDCl 3, 400 MHz, 23 o C). Figure S51. 13 C{ 1 H} NMR spectrum of 7o (CDCl 3, 100 MHz, 23 o C). S40

Figure S52. 1 H NMR spectrum of 7p (CDCl 3, 400 MHz, 23 o C). Figure S53. 13 C{ 1 H} NMR spectrum of 7p (CDCl 3, 100 MHz, 23 o C). S41

Figure S54. 1 H NMR spectrum of 7q (CDCl 3, 400 MHz, 23 o C). Figure S55. 13 C{ 1 H} NMR spectrum of 7q (CDCl 3, 100 MHz, 23 o C). S42

Figure S56. 1 H NMR spectrum of 7r (CDCl 3, 400 MHz, 23 o C). Figure S57. 13 C{ 1 H} NMR spectrum of 7r (CDCl 3, 100 MHz, 23 o C). S43

Figure S58. 1 H NMR spectrum of 9a (CDCl 3, 400 MHz, 23 o C). Figure S59. 13 C{ 1 H} NMR spectrum of 9a (CDCl 3, 100 MHz, 23 o C). S44

Figure S60. 1 H NMR spectrum of 9b (CDCl 3, 400 MHz, 23 o C). Figure S61. 13 C{ 1 H} NMR spectrum of 9b (CDCl 3, 100 MHz, 23 o C). S45

Figure S62. 1 H NMR spectrum of 9c (DMSO-d 6, 400 MHz, 23 o C). Figure S63. 13 C{ 1 H} NMR spectrum of 9c (DMSO-d 6, 100 MHz, 23 o C). S46

Figure S64. 1 H NMR spectrum of 9d (CDCl 3, 400 MHz, 23 o C). Figure S65. 13 C{ 1 H} NMR spectrum of 9d (CDCl 3, 100 MHz, 23 o C). S47

Figure S66. 1 H NMR spectrum of 9e (CDCl 3, 400 MHz, 23 o C). Figure S67. 13 C{ 1 H} NMR spectrum of 9e (CDCl 3, 100 MHz, 23 o C). S48

Figure S68. 1 H NMR spectrum of 9f (CDCl 3, 400 MHz, 23 o C). Figure S69. 13 C{ 1 H} NMR spectrum of 9f (CDCl 3, 100 MHz, 23 o C). S49

Figure S70. 1 H NMR spectrum of 9g (CDCl 3, 400 MHz, 23 o C). Figure S71. 13 C{ 1 H} NMR spectrum of 9g (CDCl 3, 100 MHz, 23 o C). S50

Figure S72. 1 H NMR spectrum of 9h (CDCl 3, 400 MHz, 23 o C). Figure S73. 13 C{ 1 H} NMR spectrum of 9h (CDCl 3, 100 MHz, 23 o C). S51

Figure S74. 1 H NMR spectrum of 9i (CDCl 3, 400 MHz, 23 o C). Figure S75. 13 C{ 1 H} NMR spectrum of 9i (CDCl 3, 100 MHz, 23 o C). S52

Figure S76. 1 H NMR spectrum of 9j (CDCl 3, 400 MHz, 23 o C). Figure S77. 13 C{ 1 H} NMR spectrum of 9j (CDCl 3, 100 MHz, 23 o C). S53

Figure S78. 1 H NMR spectrum of 9k (CDCl 3, 400 MHz, 23 o C). Figure S79. 13 C{ 1 H} NMR spectrum of 9k (CDCl 3, 100 MHz, 23 o C). S54

Figure S80. 1 H NMR spectrum of 9l (CDCl 3, 400 MHz, 23 o C). Figure S81. 13 C{ 1 H} NMR spectrum of 9l (CDCl 3, 100 MHz, 23 o C). S55

Figure S82. 1 H NMR spectrum of 9m (CDCl 3, 400 MHz, 23 o C). Figure S83. 13 C{ 1 H} NMR spectrum of 9m (CDCl 3, 100 MHz, 23 o C). S56

Figure S84. 1 H NMR spectrum of 9n (CDCl 3, 400 MHz, 23 o C). Figure S85. 13 C{ 1 H} NMR spectrum of 9n (CDCl 3, 100 MHz, 23 o C). S57

Figure S86. 1 H NMR spectrum of 11a (CDCl 3, 400 MHz, 23 o C). Figure S87. 13 C{ 1 H} NMR spectrum of 11a (CDCl 3, 100 MHz, 23 o C). S58

Figure S88. 1 H NMR spectrum of 11b (CDCl 3, 400 MHz, 23 o C). Figure S89. 13 C{ 1 H} NMR spectrum of 11b (CDCl 3, 100 MHz, 23 o C). S59

Figure S90. 1 H NMR spectrum of 12a (DMSO-d 6, 400 MHz, 23 o C). Figure S91. 13 C{ 1 H} NMR spectrum of 11b (DMSO-d 6, 100 MHz, 23 o C). S60

Figure S92. 1 H NMR spectrum of 12b (DMSO-d 6, 400 MHz, 23 o C). Figure S93. 13 C{ 1 H} NMR spectrum of 12b (DMSO-d 6, 100 MHz, 23 o C). S61

Figure S94. 1 H NMR spectrum of 14a (CDCl 3, 400 MHz, 23 o C). Figure S95. 13 C{ 1 H} NMR spectrum of 14a (CDCl 3, 100 MHz, 23 o C). S62

Figure S96. 1 H NMR spectrum of 14b (CDCl 3, 400 MHz, 23 o C). Figure S97. 13 C{ 1 H} NMR spectrum of 14b (CDCl 3, 100 MHz, 23 o C). S63

Figure S98. 1 H NMR spectrum of 14c (CDCl 3, 400 MHz, 23 o C). Figure S99. 13 C{ 1 H} NMR spectrum of 14c (CDCl 3, 100 MHz, 23 o C). S64

Figure S100. 1 H NMR spectrum of 14d (CDCl 3, 400 MHz, 23 o C). Figure S101. 13 C{ 1 H} NMR spectrum of 14d (CDCl 3, 100 MHz, 23 o C). S65

Figure S102. 1 H NMR spectrum of 14e (CDCl 3, 400 MHz, 23 o C). Figure S103. 13 C{ 1 H} NMR spectrum of 14e (CDCl 3, 100 MHz, 23 o C). S66

Figure S104. 1 H NMR spectrum of 14f (CDCl 3, 400 MHz, 23 o C). Figure S105. 13 C{ 1 H} NMR spectrum of 14f (CDCl 3, 100 MHz, 23 o C). S67

Figure S106. 1 H NMR spectrum of 14g (CDCl 3, 400 MHz, 23 o C). Figure S107. 13 C{ 1 H} NMR spectrum of 14g (CDCl 3, 100 MHz, 23 o C). S68

Figure S108. 1 H NMR spectrum of 14h (CDCl 3, 400 MHz, 23 o C). Figure S109. 13 C{ 1 H} NMR spectrum of 14h (CDCl 3, 100 MHz, 23 o C). S69

Figure S110. 1 H NMR spectrum of 14i (CDCl 3, 400 MHz, 23 o C). Figure S111. 13 C{ 1 H} NMR spectrum of 14i (CDCl 3, 100 MHz, 23 o C). S70

Figure S112. 1 H NMR spectrum of 14j (CDCl 3, 400 MHz, 23 o C). Figure S113. 13 C{ 1 H} NMR spectrum of 14j (CDCl 3, 100 MHz, 23 o C). S71

Figure S114. 1 H NMR spectrum of 14k (CDCl 3, 400 MHz, 23 o C). Figure S115. 13 C{ 1 H} NMR spectrum of 14k (CDCl 3, 100 MHz, 23 o C). S72

Figure S116. 1 H NMR spectrum of 14l (CDCl 3, 400 MHz, 23 o C). Figure S117. 13 C{ 1 H} NMR spectrum of 14l (CDCl 3, 100 MHz, 23 o C). S73

Figure S118. 1 H NMR spectrum of 14m (CDCl 3, 400 MHz, 23 o C). Figure S119. 13 C{ 1 H} NMR spectrum of 14m (CDCl 3, 100 MHz, 23 o C). S74

Figure S120. 1 H NMR spectrum of 14n (CDCl 3, 400 MHz, 23 o C). Figure S121. 13 C{ 1 H} NMR spectrum of 14n (CDCl 3, 100 MHz, 23 o C). S75

Figure S122. 1 H NMR spectrum of 14o (CDCl 3, 400 MHz, 23 o C). Figure S123. 13 C{ 1 H} NMR spectrum of 14o (CDCl 3, 100 MHz, 23 o C). S76

Figure S124. 1 H NMR spectrum of 14p (CDCl 3, 400 MHz, 23 o C). Figure S125. 13 C{ 1 H} NMR spectrum of 14p (CDCl 3, 100 MHz, 23 o C). S77

Figure S126. 1 H NMR spectrum of 14q (CDCl 3, 400 MHz, 23 o C). Figure S127. 13 C{ 1 H} NMR spectrum of 14q (CDCl 3, 100 MHz, 23 o C). S78

Figure S128. 1 H NMR spectrum of 14r (CDCl 3, 400 MHz, 23 o C). Figure S129. 13 C{ 1 H} NMR spectrum of 14r (CDCl 3, 100 MHz, 23 o C). S79