Supporting Information

Supporting Information Figure S1.1 Positive HR-ESI-MS spectrum of compound 1 Figure S1.2 IR spectrum of compound 1 Figure S1.3 1 H NMR (600 MHz, D 2 O) spectrum of compound 1 Figure S1.4 1 H NMR (600 MHz, DMSO-d 6 ) spectrum of compound 1 Figure S1.5 13 C NMR (150 MHz, D 2 O) spectrum of compound 1 Figure S1.6 HMQC (D 2 O) spectrum of compound 1 Figure S1.7 HMBC (D 2 O) spectrum of compound 1 Figure S1.8 Impurity peaks present in compound 1 as detected by HMQC (up) and HMBC spectrum (down) Figure S2.1 Positive HR-ESI-MS spectrum of compound 2 Figure S2.2 Negative HR-ESI-MS spectrum of compound 2 Figure S2.3 1 H NMR (600 MHz, D 2 O) spectrum of compound 2 ( H 2.63 is the signal of DMSO, H 8.35 is the signal of formamide derived from polyamide column chromatography) Figure S2.4 13 C NMR (150 MHz, D 2 O) spectrum of compound 2 ( C 38.7 is the signal of DMSO, C 170.8 is the signal of formamide derived from polyamide column chromatography) Figure S2.5 HMQC (D 2 O) spectrum of compound 2 Figure S2.6 HMBC (D 2 O) spectrum of compound 2 Figure S2.7 Impurity peaks present in compound 2 as detected by HMQC (up left) and HMBC spectrum (up right and down) Figure S3.1 Positive HR-ESI-MS spectrum of compound 3 Figure S3.2 1 H NMR (600 MHz, D 2 O) spectrum of compound 3 ( H 8.35 is the signal of formamide derived from polyamide column chromatography) Figure S3.3 13 C NMR (150 MHz, D 2 O) spectrum of compound 3 ( C 170.6 is the signal of formamide derived from polyamide column chromatography) Figure S3.4 HMQC (D 2 O) spectrum of compound 3 Figure S3.5 HMBC (D 2 O) spectrum of compound 3 Figure S3.6 Impurity peaks present in compound 3 as detected by HMBC spectrum Figure S4.1 Positive HR-ESI-MS spectrum of compound 4

Figure S4.2 Negative HR-ESI-MS spectrum of compound 4 Figure S4.3 1 H NMR (600 MHz, D 2 O) spectrum of compound 4 Figure S4.4 1 H- 1 HCOSY spectrum of compound 4 Figure S4.5 13 C NMR (150 MHz, D 2 O) spectrum of compound 4 Figure S4.6 DEPT spectrum of compound 4 Figure S4.7 HMQC spectrum of compound 4 Figure S4.8 HMBC spectrum of compound 4 Figure S4.9 Impurity peaks present in compound 4 as detected by HMQC (up) and HMBC spectrum (down) Physiochemical and spectroscopic data of known compounds 6-12.

Figure S1.1 Positive HR-ESI-MS spectrum of o compound 1 Figure S1.2 IR spectrum of compound 1

Figure S1.3 1 H NMR (600 MHz, D 2 O) spectrum of compound 1 Figure S1.4 1 H NMR (600 MHz, DMSO-d 6 ) spectrum of compound 1

Figure S1.5 13 C NMR (150 MHz, D 2 O) spectrum of compound 1 Figure S1.6 HMQC (D 2 O) spectrum of compound 1

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 f1 (ppm) 8.5 7.5 6.5 5.5 4.5 f2 (ppm) 3.5 2.5 1.5 Figure S1.7 HMBC (D 2 O) spectrum of compound 1 Figure S1.8 Impurity peaks present in compound 1 as detected by HMQC (up) and HMBC spectrum (down)

Figure S2.1 Positive HR-ESI-MS spectrum of compound 2 Figure S2.2 Negative HR-ESI-MS spectrum of compound 2

8.350 7.944 7.436 7.349 6.815 6.780 4.702 3.685 3.675 3.665 2.873 2.630 6500 6000 5500 5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0 0.78 0.85 1.00 1.02 1.00 1.10 2.27 2.13 2.10-500 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 f1 (ppm) Figure S2.3 1 H NMR (600 MHz, D 2 O) spectrum of compound 2 ( H 2.63 is the signal of DMSO, H 8.35 is the signal of formamide derived from polyamide column chromatography) Figure S2.4 13 C NMR (150 MHz, D 2 O) spectrum of compound 2 ( C 38.7 is the signal of DMSO, C 170.8 is the signal of formamide derived from polyamide column chromatography)

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 8.5 7.5 6.5 5.5 f2 (ppm) 4.5 3.5 2.5 Figure S2.5 HMQC (D 2 O) spectrum of compound 2 8.5 7.5 6.5 5.5 4.5 f2 (ppm) 3.5 2.5 1.5 Figure S2.6 HMBC (D 2 O) spectrum of compound 2 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190

Figure S2.7 Impurity peaks present in compound 2 as detected by HMQC (up left) and HMBC spectrum (up right and a down) Figure S3.1 Positive HR-ESI-MS spectrum of o compound 3

8.509 8.348 7.530 7.119 6.763 6.631 6.626 6.460 6.456 4.994 4.703 3.818 3.804 3.791 2.998 2.985 2.972 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 0 1.07 1.30 1.00 1.00 1.00 1.00 1.01 2.01 2.02 0.34 2.13 0.33-200 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 f1 (ppm) Figure S3.2 1 H NMR (600 MHz, D 2 O) spectrum of compound 3 ( H 8.35 is the signal of formamide derived from polyamide column chromatography) 170.64 163.78 144.94 144.82 144.00 132.86 119.90 115.88 115.54 112.78 111.06 54.94 47.28 24.57 2100 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 f1 (ppm) Figure S3.3 13 C NMR (150 MHz, D 2 O) spectrum of compound 3 ( C 170.6 is the signal of formamide derived from polyamide column chromatography)

10 20 30 40 50 60 70 80 90 100 110 120 130 140 f1 (ppm) 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 f2 (ppm) 5.0 4.5 4.0 3.5 3.0 2.5 Figure S3.4 HMQC (D 2 O) spectrum of compound 3 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 f1 (ppm) 9.0 8.0 7.0 6.0 f2 (ppm) 5.0 4.0 3.0 Figure S3.5 HMBC (D 2 O) spectrum of compound 3

Figure S3.6 Impurity peaks present in compound 3 as detected by HMBC spectrum Figure S4.1 Positive HR-ESI-MS spectrum of o compound 4 Figure S4.2 Negative HR-ESI-MS spectrum of compound 4

Figure S4.3 1 H NMR (600 MHz, D 2 O) spectrum of compound 4 Figure S4.4 1 H- 1 HCOSY spectrum of compound 4

Figure S4.5 13 C NMR (150 MHz, D 2 O) spectrum of compound 4 Figure S4.6 DEPT spectrum of compound 4

Figure S4.7 HMQC spectrum of compound 4 Figure S4.8 HMBC spectrum of compound 4

Figure S4.9 Impurity peaks present in compound 4 as detected by HMQC (up) and HMBC spectrum (down) Physiochemical and spectroscopicc data of known compounds 6-12. 6,7-Dihydroxy-1-methyl-3,4-dihydroisoquinoline (6): yellow powder; HRESIMS: m/z 178.0859 [M+H] + (calcd. for C 10 H 12 NO 2, 178.0868); 1 H NMR (600 MHz, DMSO-d 6 ) δ: 7.12 (1H, s, H-8), 6.61 (1H, s, s H-5), 3.58 (2H, t, J 7.8 Hz, H-3), 2.777 (2H, t, J 7.8 Hz, H-4), 2.47 (3H, s, H-1 ); 13 C NMR (150 MHz, DMSO-d 6 ) δ: 161.2 (C-1), 152.11 (C-6), 145.7 (C-7), 132.4 (C-9a), 126.4 (C-10b), 115.3 (C-8), 115.0 (C-5), 41.9 (C-3), 25.2 (C-4), 20.3 (C-1 ). 6,7-Dihydroxy-3,4-dihydroisoquinoline (7): yellow powder; HRESIMS: m/z 164.0704 [M+ +H] + (calcd. for C 9 H 10 0NO 2, 164. 0712); 1 H NMR (6000 MHz, D 2 O) δ: 8.05 (1H, s, H-1), 6.84 (1H, s, H-8), 6.37 ( 1H, s, H-5), 3.55 (2H, t, J 7.8 Hz, H-3), 2.79 (2H, t, J 7.8 Hz, H-4) ; 13 C NMR (150 MHz, D 2 O) δ: 166.9 (C-1), 160.6 (C-6), 145.8 (C-7), 135.8 (C-9a), 117.2 (C-10b), 117.1 (C-8), 110.8 (C-5), 40.6 (C-3), 24.6 (C-4).

(S)-(-)-salsolinol (8): yellow powder; [α] 20 D 32 (c 0.1, MeOH); ESIMS: m/z 180 [M+H] + ; 1 H NMR (600 MHz, D 2 O) δ: 6.67 (1H, s, H-8), 6.64 (1H, s, H-5), 4.42 (1H, q, J 6.6 Hz, H-1), 3.44 (1H, m, H-3a), 3.29 (1H, m, H-3b), 2.92 (1H, m, H-4a), 2.85 (1H, m, H-4b), 1.51 (3H, d, J 6.6 Hz, H-1 ); 13 C NMR (150 MHz, D 2 O) δ: 143.8 (C-6), 143.1 (C-7), 125.2 (C-10b), 123.5 (C-9a), 115.7 (C-5), 113.2 (C-8), 50.8 (C-1), 39.3 (C-3), 24.1 (C-4), 18.6(C-1 ). (R)-(+)-1-isobutyl-6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline (9): yellow powder; [α] 20 D +12 (c 0.1, MeOH); positive HRESIMS: m/z 222.1487 [M+H] + (calcd. for C 13 H 20 NO 2, 222.1494); negative HRESIMS: m/z 220.1343[M-H] - (calcd. for C 13 H 18 NO 2, 220.1338); 1 H NMR (600 MHz, D 2 O) δ: 6.63 (1H, s, H-8), 6.62 (1H, s, H-5), 4.34 (1H, q, J 6.6 Hz, H-1), 3.43 (1H, m, H-3a), 3.23 (1H, m, H-3b), 2.87 (2H, m, H-4), 1.68 (2H, m, H-1 ), 1.68 (1H, m, H-2 ), 0.92 (3H, d, J 5.4 Hz, H-3 ), 0.90 (3H, d, J 5.4 Hz, H-4 ); 13 C NMR (150 MHz, D 2 O) δ: 143.7 (C-6), 142.9 (C-7), 124.6 (C-10b), 123.6 (C-9a), 115.7 (C-5), 113.6 (C-8), 52.9 (C-1), 38.9 (C-3), 23.9 (C-4), 42.8 (C-1 ), 23.8 (C-2 ), 20.5 (C-3 ), 22.2 (C-4 ). (R)-(+)-1-benzyl-6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline (10): yellow powder; [α] 20 D +3 (c 0.1, MeOH); positive HRESIMS: m/z 256.1335 [M+H] + (calcd. for C 16 H 18 NO 2, 256.1338); negative HR-ESI-MS: m/z 254.1193 [M-H] - (calcd. for C 16 H 16 NO 2, 254.1181), 509.2472 [2M-H] - (calcd. for C 32 H 33 N 2 O 4, 509.2440); 1 H NMR (600 MHz, D 2 O) δ: 7.36 (2H, d, J 7.8 Hz, H-3, 5 ), 7.31 (1H, t, J 7.8 Hz, H-4 ), 7.24 (2H, t, J 7.8 Hz, H-2, 6 ), 6.67 (1H, s, H-5), 6.61 (1H, s, H-8), 4.62 (1H, dd, J 1 9.6 Hz, J 2 6.0 Hz, H-1), 3.43 (1H, m, H-3a), 3.40 (1H, m, H-7 a), 3.21 (1H, m, H-3b), 2.99 (1H, m, H-7 b), 2.93 (1H, m, H-4a), 2.86 (1H, m, H-4b); 13 C NMR (150 MHz, D 2 O) δ: 144.1 (C-6), 142.8 (C-7), 135.0 (C-1 ), 129.5 (C-2,6 ), 129.2 (C-3,5 ), 127.8 (C-4 ), 123.7 (C-9a), 123.2 (C-10b), 115.8 (C-5), 113.8 (C-8), 56.2 (C-1), 39.3 (C-3), 39.2 (C-7 ), 24.0 (C-4). Dopamine (11): white powder; HRESIMS: m/z 154.0859 [M+H] + (calcd. for C 8 H 12 NO 2 154.0868); 1 H NMR (600 MHz, D 2 O) δ: 6.68 (1H, d, J 7.8 Hz, H-5), 6.61 (1H, d, J 1.8 Hz, H-2), 6.49 (1H, dd, J 1 7.8 Hz, J 2 1.8 Hz, H-6), 2.95 (2H, t, J 7.8 Hz, H-8), 2.68 (2H, t, J 7.8 Hz, H-7); 13 C NMR (150 MHz, D 2 O) δ: 145.8

(C-3), 144.6 (C-4), 128.3 (C-1), 119.7 (C-6), 116.4 (C-2), 116.1 (C-5), 40.9 (C-2 ), 33.1 (C-1 ). 2-Sulfonic acid dopamine (12): white powder; positive HRESIMS: m/z 234.0428 [M+H] + (calcd. for C 8 H 12 NO 5 S, 234.0436); negative HRESIMS: m/z 232.0287 [M-H] - (calcd. for C 8 H 10 NO 5 S, 232.0280), 465.0651 [2M-H] - (calcd. for C 16 H 21 N 2 O 10 S 2, 465.0638); 1 H NMR (600 MHz, DMSO-d 6 ) δ: 6.70 (1H, d, J 8.4 Hz, H-5), 6.50 (1H, d, J 8.4 Hz, H-6), 3.15 (2H, t, J 7.2 Hz, H-7), 3.03 (2H, t, J 7.2 Hz, H-8); 13 C NMR (150 MHz, DMSO-d 6 ) δ: 129.5 (C-1), 126.2 (C-2), 143.4 (C-3), 145.2 (C-4), 116.2 (C-5), 120.8 (C-6), 41.2 (C-2 ), 31.3 (C-1 ).