Supporting Information

Supporting Information Biomimetic total syntheses of borreverine and flinderole alkaloids. Dattatraya. Dethe,* Rohan D. Erande and Alok Ranjan Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur-208016, India. Tel: + 91-512-2596537, fax: + 91-512-2597436. 1

Table of Contents: MR data comparisons of isoborreverine (5):...3 MR data comparisons of dimethylisoborreverine (6):...4 MR data comparisons of flinderole A (1):...5 MR spectra of compound 22, 22a, 19, 24, 25a, 25b, 25c, 25 and 23a:...6 OESY of compound 23a:...18 MR spectra of compound 23b:...19 Crystal structure of compound (23b):...20 CIF file of compound (23b):...21 MR spectra of comp. 26, 27, 28a, 28b, 34, 35, 36, 38, 32, 39a, 39b, 40a, 40b and 45:...22 MR spectra of dimethylisoborreverine (6) in DMSO-d 6 :...41 MR spectra of dimethylisoborreverine (6) in CDCl 3 :...42 MR spectra of TFA salt of dimethylisoborreverine (6) in DMSO-d 6 :...43 1 MR spectra comparisons of dimethylisoborreverine (6):...44 13 C MR spectra comparisons of dimethylisoborreverine (6):...45 MR spectra of TFA salt isoborreverine (5):...46 MR spectra of isoborreverine (5) in DMSO-d 6 :...47 1 MR spectra comparisons of isoborreverine (5):...48 13 C MR spectra comparisons of isoborreverine (5):...49 MR spectra of isoborreverine (5) in CDCl 3 :...50 MR spectra of compound 46a:...51 MR spectra of flinderole A (1):...52 1 MR spectra comparisons of flinderole A (1):...54 1 MR spectra comparisons of TFA salt flinderole A (1):...55 13 C MR spectra comparisons of TFA salt flinderole A (1):...56 MR spectra of compound 46b:...57 MR spectra of desmethyl flinderole (C):...58 MR spectra comparisons of desmethyl flinderole (C):...60 MR spectra of compound 48, 49, 50, 51, 52, 53, 10, 54a and 54:...61 2

C atural isoborrevrine F. Tillequin, M. Koch J. at. Prod., 48, 120 (1985). atural isoborreverine A. M. Balde et al., Phytochemistry, 15, 997 (1991). Synthetic isoborrevrine Position δc (CDCl 3, 20 Mz) δc (CDCl 3, 50.10 Mz) δc (CDCl 3, 100 Mz) 2 133.9 133.4 133.3 3 55.4 53.9 54.5 5 52.9 52.1 52.6 6 25.2 25.1 25.1 7 111.7 111.3 111.8 8 129.3 129.2 128.9 9 119.1 119.6 119.6 10 119.5 119.6 119.0 11 121.1 121.2 121.3 12 110.2 110.3 110.2 13 134.4 134.3 134.0 14 59.5 59.6 59.6 15 32.7 32.9 32.5 16 28.1 24.0 24.5 17 29.1 29.1 29.5 18 35.9 36.0 36.6 2 143.6 143.5 143.4 3 38.1 38.3 37.7 5 53.2 53.0 53.1 6 25.5 25.3 26.0 7 103.3 103.0 103.1 8 133.5 133.4 132.8 9 119.5 119.6 119.6 10 119.9 119.6 119.6 11 122.8 122.8 122.8 12 112.1 112.2 112.7 13 137.6 137.7 136.8 14 120.4 120.0 119.9 15 133.6 133.4 133.2 16 41.5 40.8 41.5 17 24.1 28.1 28.0 18 36.1 36.1 36.9 3

10 4 17 16' 17' 8 6 14' 4' 12 16' 6' 11' 9' Dimethyl isoborreverine (6) atural dimethyl isoborreverine (DMSO-d 6 ) Synthetic dimethyl isoborrevrine (DMSO-d 6 ) atural dimethyl isoborrevrine (DMSO-d 6 ) Synthetic dimethyl isoborrevrine (DMSO-d 6 ) Liza Sylvia Fernandez, Griffith University, Ph.D. thesis, (2009) Liza Sylvia Fernandez, Griffith University, Ph.D. thesis, (2009) Position δc (150 Mz) (Chemical shifts determined from 2D MR experiments) δc (125 Mz) δ (600 Mz) (mult, J z) δ (500 Mz) (mult, J z) 1 () 11.17 (brs) 11.21 (brs) 2 133.4 133.9 3 53.3 53.5 5.49 (d, 9.0) 5.49 (d, 9.5) 4 () 9.90 (brs) 10.20 (brs) 4 Me 41.8 42.1 2.95 2.92 5 56.2 56.1 3.24 (m)a, 3.35 (m)b 3.33 (m)a, 3.34 (m)b 6 19.3 19.3 3.14, 3.18 3.12, 3.18 7 107.3 107.2 8 126.9 126.9 9 118.3 118.5 7.68 (d, 7.8) 7.67 (d, 7.6) 10 118.5 118.7 7.06 (dd, 7.8, 7.8) 7.02 (dd, 7.6, 7.0) 11 121.9 121.7 7.11 (dd, 7.8, 7.8) 7.09 (dd, 7.6, 7.3) 12 111.1 111.3 7.29 (d, 7.8) 7.28 (d, 7.9) 13 135.7 135.8 14 56.9 57.1 3.14 (m) 3.14 (m) 15 31.5 31.4 16 27.2 27.4 0.69 (s) 0.69 (s) 17 28 28.2 1.04 (s) 1.04 (s) 2 142.9 142.9 3 36.1 36.2 4.11 (m) 4.11 (m) 4 () 9.79 (brs) 10.10 (brs) 4 Me 41.8 42.1 2.85 2.82 5 56.3 56.6 3.24 (m)a, 3.35 (m)b 3.33 (m)a, 3.34 (m)b 6 19.3 3.14, 3.18 3.12, 3.18 7 99.2 99.0 8 131.1 131.3 9 117.8 118.1 7.53 (d, 7.8) 7.52 (d, 7.9) 10 118.4 118.5 6.91 (dd, 7.8, 7.8) 6.88 (dd, 7.3, 7.3) 11 119.9 120.2 6.73 (dd, 7.8, 7.8) 6.71 (dd, 7.6, 7.3) 12 108.8 108.9 6.23 (d, 7.8) 6.22 (d, 7.9) 13 131.6 131.8 14 118.5 118.9 5.47 (brm) 5.46 (brm) 15 132.2 132.1 16 39.8 41.9, 41.8 1.71 (m), 2.28 (d, 17.4) 1.72 (m), 2.28 (d, 14.0) 17 23.4 23.5 1.70 (brs) 1.69 (brs) 4

atural Flinderole A (TFA salt in DMSO-d 6 ) Synthetic Flinderole A (TFA salt in DMSO-d 6 ) atural Flinderole A (TFA salt in DMSO-d 6 ) Synthetic Flinderole A (TFA salt in DMSO-d 6 ) V. M. Avery et al., Org. Lett., 11, 329 (2009). V. M. Avery et al., Org. Lett., 11, 329 (2009). Position δc (150 Mz) (Chemical shifts determined from 2D experiments) δc (125 Mz) δ (600 Mz) (mult, J z) δ (500 Mz) (mult, J z) 1 () 11.08 (s) 11.14 (s) 2 132.4 132.4 3 116.4 116.4 6.56 (d, 16.2) 6.58 (d, 16.3) 4 () 8.60 (m)a 8.84 (m)a 8.54 (m)b 8.78 (m)b 4 Me 32.5 32.4 2.62 (t, 5.4) 2.62 (t, 5.4) 5 48.83 48.82 2.99 (m, 2) d 2.99 (m, 2) d 6 20.2 b 20.2 b 3.01 (m)a e 3.01 (m)a e 2.90 (brt, 7.5)b f 2.90 (brt, 8.0)b f 7 109.1 109.2 8 127.6 127.6 9 118.2 c 118.2 c 7.53 (brd, 7.5) 7.54 (brd, 8.0) 10 118.8 118.8 6.98 (dd, 7.5, 7.5) 6.98 (dd, 7.4, 7.4) 11 122.4 122.4 7.08 (dd, 7.5, 7.5) 7.08 (dd, 7.7, 7.7) 12 110.8 110.8 7.24 (brd, 7.5) 7.25 (brd, 7.7) 13 136.4 136.4 14 50.6 50.6 2.90 (dd, 13.2, 8.0)β f 2.90 (dd, 12.9, 8.0)β f 2.31 (dd, 13.2, 7.5)α 2.31 (dd, 12.6, 7.7)α 15 63.2 63.3 16 132.1 132.1 6.50 (d, 16.2) 6.52 (d, 16.3) 17 24.7 24.6 1.94 (s) 1.96 (s) 2 143.6 143.6 3 34.5 34.5 4.28 (ddd, 9.6, 8.0, 7.5) 4.30 (ddd, 8.9, 8.3, 8.0) 4 () 8.48 (m, 2) 8.78 (m, 2) 4 Me 32.4 32.3 2.56 (brt, 5.4) 2.56 (brt, 5.2) 5 48.79 48.8 2.99 (m, 2) d 2.99 (m, 2) d 6 20.3 b 20.3 b 3.01 (m) a e 3.01 (m) a e 2.90 (brt, 7.5)b f 2.90 (brt, 8.0)b f 7 100.2 100.3 8 132.2 132.2 9 118.2 c 118.3 c 7.56 (d, 7.5) 7.58 (d, 7.7) 10 118.6 118.6 7.02 (dd, 7.5, 7.5) 7.02 (dd, 6.3, 6.3) 11 120.3 120.3 7.04 (dd, 7.5, 7.5) 7.04 (dd, 6.3, 6.3) 12 110.1 110.1 7.41 (d, 7.5) 7.43 (d, 7.4) 13 130.9 130.9 14 125.0 124.9 5.32 (dsept., 9.6, 1.3) 5.32 (dsept., 8.9, 1.2) 15 133.0 133.1 16 18.0 18.0 1.84 (d, 1.3) 1.85 (d, 1.3) 17 25.4 25.4 1.80 (d, 1.3) 1.80 (d, 1.3) 5

RPALC_1-4.JDF 8.08 8.07 7.79 7.78 7.44 7.40 7.38 7.35 7.33 7.32 7.27 7.24 7.22 5.46 4.84 3.52 2.89 2.87 2.86 2.84 2.73 2.72 2.70 2.69 2.31 1.79 O SO 2 Ph 18 1.00 2.04 1.05 1.04 2.08 1.17 1.01 1.06 2.15 0.92 1.08 1.07 3.10 3.15 RPALC_13C-3.JDF CLOROFORM-d 141.93 137.90 137.52 136.63 133.56 131.26 128.96 126.34 125.16 123.75 120.27 119.11 115.14 113.73 77.26 77.00 76.75 65.75 45.54 22.14 9.71 O SO 2 Ph 18 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 6

TMS 8.07 8.04 7.61 7.59 7.42 7.40 7.40 7.38 7.36 7.29 7.27 7.25 4.90 4.82 3.79 2.19 1.80 0.00 1.00 2.01 6.70 1.00 1.03 2.08 3.14 3.20 CLOROFORM-d 195.54 138.89 137.08 135.75 134.95 133.78 131.66 128.58 127.30 127.18 127.06 124.82 120.72 116.05 115.25 77.63 77.00 76.36 53.16 22.65 9.27 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 7

133.92 128.70 127.44 127.18 124.95 120.85 116.18 115.37 53.28 22.78 9.40 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 8.06 8.04 7.72 7.70 7.41 7.40 7.39 7.38 7.37 7.32 7.30 7.25 7.23 6.56 2.27 2.23 1.98 TMS 1.00 2.02 6.42 0.98 3.06 3.19 3.12 8

CLOROFORM-d 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 133.72 128.69 127.20 126.96 126.03 124.57 120.52 115.97 28.09 21.12 9.44 186.76 155.58 137.17 136.85 135.88 133.59 131.67 128.57 127.09 126.83 125.92 125.59 124.45 120.40 115.85 77.63 77.00 76.36 27.96 21.00 9.31 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 9

R732_11O_E14.ALS 6.64 6.62 6.50 6.48 6.26 6.26 6.24 6.20 6.18 6.18 4.30 4.28 4.26 3.92 3.92 3.88 3.88 1.79 1.77 1.75 1.73 1.67 1.65 1.64 1.62 1.41 0.88 1.11 1.09 1.07 1.03 1.00 2.06 2.34 3.15 3.07 R732_13C-2.JDF ACETOITRILE-d3 ACETOITRILE-d3 143.50 138.00 136.59 129.92 122.25 119.59 119.21 118.40 113.62 111.80 107.06 65.43 46.39 22.72 8.70 1.89 1.73 1.56 1.39 1.23 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 10

Wed2av400#003.001.001.1r.esp TMS 8.09 8.07 7.81 7.79 7.49 7.45 7.43 7.39 7.38 7.32 7.32 7.27 7.25 4.89 3.25 2.25 0.00 1.02 2.09 6.76 2.00 1.05 3.13 Sat2av2#043.002.001.1r.esp CLOROFORM-d 138.44 136.07 134.92 133.74 130.67 129.21 126.21 125.41 123.60 119.52 119.41 114.40 77.64 77.00 76.37 54.96 8.90 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 11

Tue4av2#079.001.001.1r.esp TMS 8.17 7.55 7.51 7.26 7.25 7.24 7.18 7.18 7.14 7.14 7.13 7.07 4.76 2.27 1.92 0.00 0.98 1.00 3.23 2.04 3.12 1.14 Fri4av2#021.002.001.1r.esp CLOROFORM-d 135.62 132.82 128.78 122.22 119.23 118.85 110.75 108.45 77.63 77.00 76.37 56.54 8.32 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 12

Wed4av400#001.001.001.1r.esp CLOROFORM-d TMS 10.04 9.15 7.71 7.69 7.39 7.38 7.36 7.25 7.17 7.16 7.16 7.15 7.14 2.64 0.00 1.01 0.98 1.00 2.031.00 3.08 Fri4av2#020.002.001.1r.esp CLOROFORM-d 180.60 137.60 132.12 128.13 127.64 125.12 121.34 120.37 112.30 77.64 77.00 76.37 8.39 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 13

Fri4av2#020.001.001.1r.esp 180.67 127.71 121.41 120.43 112.37 8.47 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Wed4av2#034.001.001.1r.esp TMS 8.49 7.85 7.77 7.58 7.54 7.28 7.25 7.25 7.24 7.14 7.13 7.10 7.10 6.22 6.14 4.35 4.31 4.28 4.24 2.40 1.38 1.35 1.31 0.00 0.99 1.001.02 3.24 1.00 2.05 3.02 3.05 14

Sat4av2#031.002.001.1r.esp CLOROFORM-d 167.47 137.42 132.33 129.95 128.98 124.98 119.84 118.67 113.71 110.96 77.64 77.00 76.37 60.57 14.33 8.88 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Sat4av2#031.001.001.1r.esp 132.42 125.07 119.93 119.89 113.79 111.06 60.66 14.42 8.98 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 15

Thu3av400#011.001.001.1r.esp TMS 7.74 7.60 7.58 7.51 7.49 7.14 7.12 7.05 7.04 7.02 6.89 6.87 6.64 6.62 5.82 5.80 4.84 4.73 4.22 4.19 4.15 4.13 4.12 3.96 3.95 3.53 3.52 3.50 2.89 2.88 2.86 2.85 2.54 2.51 2.50 2.48 2.35 1.80 1.25 1.24 1.22 0.00 1.08 1.02 1.05 3.14 1.09 1.05 1.00 1.01 1.05 1.05 2.10 1.06 1.03 1.06 1.11 6.42 3.19 3.45 Fri1av2#077.002.001.1r.esp 172.42 142.50 141.83 135.92 134.10 132.53 131.36 129.33 122.46 121.15 119.52 118.92 118.55 114.42 111.15 110.03 109.97 102.51 77.75 77.12 76.49 61.51 60.28 55.91 42.29 39.29 22.62 14.21 8.84 8.52 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 16

Fri1av2#077.001.001.1r.esp 122.46 121.15 119.52 118.92 118.55 114.43 111.15 109.97 61.51 60.28 55.91 42.29 39.29 22.62 14.21 8.85 8.53 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 17

18

Thu3av400#012.001.001.1r.esp CLOROFORM-d 2O TMS 7.53 7.52 7.50 7.44 7.25 7.09 7.09 7.06 7.04 6.92 6.73 6.71 6.07 6.05 4.85 4.80 4.18 4.17 3.85 3.84 3.83 3.81 3.76 3.75 3.62 3.61 3.60 2.87 2.86 2.83 2.82 2.39 2.35 2.34 1.79 1.56 0.80 0.78 0.76 0.00 CO 2 Et 19b 2.21 1.04 4.25 1.18 0.99 1.02 2.22 1.26 1.07 1.02 0.99 1.10 6.03 1.01 3.21 3.21 Fri3av400#015.003.001.1r.esp CLOROFORM-d 171.10 142.82 141.71 135.64 133.94 131.81 128.92 128.63 122.25 121.04 119.30 119.12 118.55 118.46 113.64 110.96 110.33 109.78 102.35 77.31 77.00 76.68 61.04 58.13 53.84 42.06 37.19 22.21 13.52 8.83 8.50 CO 2 Et 19b 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 19

Fri3av400#015.002.001.1r.esp 122.29 121.07 119.33 119.15 118.59 118.50 113.68 111.00 109.82 61.07 58.17 53.88 42.10 37.22 22.25 13.56 8.88 8.54 CO 2 Et 19b 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 20

21

Tue2av400#001.001.001.1r.esp TMS 7.70 7.55 7.54 7.51 7.49 7.14 7.12 7.11 7.11 7.10 7.05 6.96 6.95 6.91 5.67 5.66 4.86 4.61 3.39 3.37 2.84 2.83 2.82 2.58 2.56 2.54 2.47 2.45 2.44 2.42 2.33 2.31 1.81 1.25 1.12 0.00 O 22 1.032.16 4.52 2.24 1.00 1.02 1.01 1.05 1.00 1.05 1.123.03 3.063.00 3.33 3.08 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 0.5 0 Fri2av2#026.002.001.1r.esp CLOROFORM-d 143.47 143.32 135.61 134.18 133.62 132.15 129.46 121.90 120.65 119.16 118.55 118.37 114.77 110.75 109.73 107.82 101.39 77.63 77.00 76.37 72.54 66.49 54.01 44.51 37.33 28.13 25.95 22.66 8.93 8.56 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 22

Fri2av2#026.001.001.1r.esp 122.00 120.75 119.26 118.65 118.47 114.88 110.85 109.83 66.59 54.11 44.62 37.43 28.23 26.05 22.77 9.04 8.67 O 22 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Mon3av400#004.001.001.1r.esp CLOROFORM-d 2O TMS 7.80 7.63 7.62 7.48 7.46 7.24 7.17 7.17 7.15 6.99 6.97 6.96 6.80 6.78 6.32 6.30 5.30 5.28 3.54 3.51 3.49 2.53 2.50 2.50 2.47 2.34 1.83 1.80 1.77 1.55 1.48 1.42 1.32 0.87 0.00 1.06 1.031.01 3.12 1.09 1.041.05 1.03 1.08 2.12 3.20 3.12 1.21 3.19 3.54 3.35 3.36 23

Mon3av2#094.002.001.1r.esp CLOROFORM-d 140.48 136.17 132.66 132.53 130.45 128.68 122.57 121.07 119.38 118.88 118.73 118.29 111.09 110.92 109.19 102.17 77.63 77.00 76.37 73.90 72.72 64.97 54.69 40.87 33.95 33.49 31.05 28.31 24.01 8.79 8.42 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Mon3av2#094.001.001.1r.esp 122.62 121.13 119.42 118.93 118.78 118.35 111.14 109.24 65.01 54.74 40.91 34.00 33.54 31.10 28.36 24.07 8.85 8.47 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 24

Fri3av2#026.001.001.1r.esp CLOROFORM-d 2O TMS 7.57 7.53 7.49 7.22 7.17 7.16 7.15 7.14 7.12 7.05 7.05 6.89 6.66 6.62 5.40 5.37 4.88 4.87 4.86 4.82 4.81 4.80 4.78 4.71 3.57 3.54 3.51 3.35 3.31 3.28 2.77 2.74 2.70 2.67 2.50 2.47 2.43 2.39 2.35 2.33 1.76 1.50-0.01 1.08 2.233.27 0.93 1.07 0.99 1.02 1.10 2.11 1.02 1.061.05 1.12 1.31 3.03 3.19 6.11 Sat3av2#077.002.001.1r.esp CLOROFORM-d 143.32 143.08 142.83 135.61 133.83 132.44 129.30 121.98 120.81 119.24 118.62 118.35 114.56 113.65 110.96 109.86 109.40 102.21 77.63 77.00 76.37 64.09 57.24 42.00 39.09 22.69 19.53 8.90 8.60 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 25

Sat3av2#077.001.001.1r.esp 122.06 120.89 119.33 118.71 118.43 114.67 113.74 111.05 109.95 64.17 57.31 42.08 39.16 22.77 19.61 8.98 8.69 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Wed4av400#015.001.001.1r.esp CLOROFORM-d 2O TMS 7.70 7.46 7.44 7.24 7.17 7.14 7.14 7.13 7.12 7.11 6.98 6.83 6.63 6.61 5.66 5.64 5.34 5.31 4.18 4.16 4.15 4.13 2.88 2.87 2.85 2.35 2.18 1.90 1.80 1.56 1.26 1.25 0.00 O 24b 1.00 1.02 1.00 3.16 1.05 1.01 0.98 1.06 1.04 1.06 1.02 3.02 3.023.063.22 6.64 11.5 11.0 10.5 10.0 9.5 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 0.5 0 26

Sat4av2#054.002.001.1r.esp CLOROFORM-d 141.48 135.98 133.56 133.45 132.08 129.16 126.03 122.21 120.60 119.28 118.94 118.76 118.12 110.94 109.57 109.40 101.87 77.64 77.00 76.37 72.47 68.39 53.98 38.47 29.08 27.13 25.71 18.37 8.76 7.76 O 24b 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 7.92 7.53 7.51 7.30 7.28 7.16 7.14 7.12 7.09 7.07 7.07 7.00 6.99 3.58 3.56 3.54 3.28 3.26 3.24 1.00 1.05 1.431.06 1.02 2.12 2.12 12.0 11.5 11.0 10.5 10.0 9.5 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 27

CLOROFORM-d 136.11 126.91 122.22 119.58 118.45 113.50 111.26 77.26 77.00 76.75 32.87 29.31 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 122.34 119.71 118.59 111.38 33.01 29.44 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 28

R680_1-4.esp 8.25 7.69 7.68 7.29 7.27 7.26 7.23 7.23 7.22 7.21 7.20 6.98 3.85 3.76 CO 2 Me 31 1.02 1.00 3.181.00 2.14 3.06 R680_13C-3.JDF CLOROFORM-d 172.84 135.96 126.93 123.27 121.86 119.39 118.52 111.25 107.66 77.26 77.00 76.75 51.87 30.97 CO 2 Me 31 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 29

R680_DEPT135-5.JDF 123.61 122.20 119.73 118.86 111.59 52.23 31.32 CO 2 Me 31 R681_1-4.JDF 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 8.46 7.55 7.54 7.53 7.53 7.16 7.15 7.15 7.14 7.12 7.11 3.78 3.73 CO 2 Me 32 Br 1.00 1.00 3.11 2.09 3.19 30

R681_13C-3.JDF CLOROFORM-d 171.85 135.90 127.28 122.27 120.17 118.03 110.63 109.76 108.00 77.26 77.00 76.75 52.14 30.79 CO 2 Me 32 Br 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 R681_DEPT135-5.JDF 122.52 120.42 118.28 110.89 52.39 31.04 CO 2 Me 32 Br 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 31

R682_1-12.JDF Water 11.06 7.38 7.37 7.25 7.23 7.04 7.03 7.01 6.93 6.91 6.90 6.60 6.57 6.41 6.38 4.77 3.74 3.32 1.26 DMSO 1.06 1.10 1.08 1.10 1.11 1.04 1.00 1.07 2.03 2.78 6.53 R682_13C-4.JDF DMSO-d6 171.81 138.81 136.19 133.73 128.27 121.85 118.71 118.33 114.02 110.66 105.93 69.38 51.61 40.01 39.84 39.67 39.51 39.34 39.17 39.01 30.18 29.44 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 32

R682_DEPT135-5.JDF DMSO-d6 138.55 121.60 118.46 118.09 113.77 110.41 51.36 40.07 39.84 39.67 39.51 39.34 39.17 39.00 29.92 29.18 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 R653_1-4.JDF 2O 9.11 7.32 7.30 7.11 7.09 6.91 6.90 6.89 6.81 6.80 6.80 6.54 6.51 6.08 6.05 3.49 3.48 3.47 3.45 2.92 2.79 2.77 2.76 2.67 2.66 2.65 1.17 0.98 1.00 0.99 1.001.00 1.001.00 2.10 0.96 2.08 1.00 6.28 33

R653_13C-2.JDF ACETOITRILE-d3 ACETOITRILE-d3 137.94 137.63 134.24 129.94 123.25 119.99 119.60 115.79 112.34 111.58 71.26 63.34 30.45 28.55 1.89 1.73 1.56 1.39 1.23 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 R653_DEPT135-3.JDF 136.96 122.27 119.01 118.61 114.81 110.60 62.36 29.47 27.57 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 34

RFIALA_1_1-4.JDF 2O ACETOITRILE-d3 9.16 7.63 7.61 7.46 7.44 7.22 7.21 7.09 7.07 7.07 7.06 7.04 6.86 6.69 6.47 6.45 5.53 5.52 4.11 3.84 3.80 3.79 3.77 3.75 3.11 3.09 3.08 3.06 3.05 3.01 2.99 2.98 2.25 2.18 1.94 1.94 1.93 1.78 1.75 1.70 1.27 1.09 0.76 0.97 1.01 1.01 1.05 2.14 1.03 1.03 1.00 1.03 0.98 1.01 4.39 3.28 2.11 1.63 1.58 1.18 3.04 1.25 3.06 3.11 RFIALA_13C-5.JDF ACETOITRILE-d3 ACETOITRILE-d3 144.06 137.22 135.08 133.74 133.64 133.49 129.37 122.96 120.95 120.30 120.08 119.51 119.37 112.03 110.30 102.89 63.31 62.86 59.21 54.90 41.23 37.92 32.68 29.26 29.14 29.00 27.68 24.04 1.89 1.73 1.56 1.39 1.23 1.07 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 35

RFIALA 135DEPT-5.JDF 121.95 119.95 119.30 119.06 118.51 118.37 111.02 109.30 62.33 61.87 58.22 53.90 40.22 36.94 28.26 28.15 28.01 26.69 23.05 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 RFID_1-4.JDF 2O ACETOITRILE-d3 9.06 7.60 7.59 7.42 7.41 7.18 7.16 7.06 7.04 7.04 7.04 7.02 6.83 6.67 6.40 6.38 5.99 5.97 5.39 5.37 5.37 4.46 4.45 4.44 4.42 3.62 3.61 3.32 3.31 3.30 3.15 3.14 3.12 2.82 2.81 2.81 2.80 2.79 2.15 1.91 1.91 1.90 1.87 1.72 1.26 1.24 1.00 0.91 1.00 1.02 1.01 2.131.01 1.02 0.96 1.00 1.02 1.00 2.15 2.25 1.06 2.09 0.91 0.94 2.07 0.92 3.07 2.38 3.07 1.09 3.21 36

RFID_13C-7.JDF ACETOITRILE-d3 ACETOITRILE-d3 144.43 137.41 135.27 133.59 133.48 131.67 129.10 123.72 122.97 120.91 120.00 119.48 119.34 118.40 112.53 112.00 110.20 102.95 72.09 64.90 63.18 62.84 54.05 39.46 30.10 29.05 28.52 28.10 26.08 18.17 1.89 1.73 1.56 1.39 1.23 1.07 O O 35b 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 R487_1-12.JDF ACETOITRILE-d3 7.50 7.44 7.42 7.23 7.22 7.06 6.99 6.99 6.98 6.98 6.95 6.27 6.24 6.01 5.98 5.29 5.29 5.27 4.24 4.22 4.21 4.19 3.65 3.44 2.84 2.83 2.81 2.80 2.79 2.78 2.76 2.70 2.62 2.19 1.94 1.92 1.77 1.77 9.22 0.97 1.01 1.03 1.00 1.01 1.10 2.99 1.001.01 1.00 1.07 2.06 2.07 2.05 1.44 1.48 1.07 1.15 1.36 3.07 6.03 37

R487_13C-3.JDF ACETOITRILE-d3 ACETOITRILE-d3 145.06 134.27 133.46 132.12 129.65 126.00 123.51 121.09 120.05 119.68 119.65 119.51 118.39 117.82 113.18 111.58 111.18 104.12 64.82 63.60 63.19 51.96 35.73 28.38 28.26 25.92 18.34 1.88 1.72 1.55 1.39 1.22 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 R_FIALC_1-4.JDF 8.26 7.56 7.55 7.30 7.28 7.25 7.25 7.23 7.18 7.09 7.06 7.04 6.71 6.68 6.31 6.27 5.28 5.26 4.30 4.29 4.27 3.83 3.82 3.82 3.81 3.81 3.80 3.79 3.02 3.01 3.00 2.95 2.91 2.71 2.70 2.69 2.40 2.38 1.84 1.78 1.76 O 36b O 1.00 2.093.65 3.31 1.01 1.00 1.01 1.05 4.13 4.411.02 1.01 3.11 3.26 3.23 38

RFIALC_13C-2.JDF CLOROFORM-d 143.58 136.36 133.46 133.18 132.42 132.26 128.65 125.00 123.21 120.44 119.72 118.84 118.73 118.06 112.24 110.61 109.98 102.41 77.25 77.00 76.74 63.23 63.05 62.90 51.69 35.24 27.59 27.29 25.69 23.18 18.15 O 36b O 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 RFIALC_135DEPT-3.JDF 132.60 125.18 123.39 120.63 119.90 119.02 118.90 118.24 110.79 110.16 63.41 63.08 51.86 35.41 27.76 27.47 25.87 23.35 18.34 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 39

R668_1-8.JDF 2O ACETOITRILE-d3 9.75 9.74 9.74 9.39 7.49 7.47 7.40 7.38 7.29 7.28 7.15 7.13 7.10 7.08 6.92 6.77 6.52 6.50 5.55 5.53 5.45 5.44 4.12 4.11 4.11 4.10 3.97 3.87 3.86 3.86 3.16 3.14 3.13 2.28 2.24 2.16 1.95 1.95 1.94 1.94 1.93 1.80 1.76 1.70 1.09 0.76 O O 41 2.02 1.08 1.08 1.02 1.09 1.14 1.26 1.14 1.09 1.00 1.09 1.22 1.14 2.13 2.12 1.16 1.46 1.28 3.29 3.41 3.47 R_668_13C-3.JDF ACETOITRILE-d3 ACETOITRILE-d3 200.44 200.31 145.42 137.20 136.08 134.23 133.47 129.25 123.50 121.59 120.62 120.19 119.87 119.71 119.18 118.39 112.28 110.46 106.29 96.56 59.25 55.04 41.07 40.25 40.21 37.86 32.65 28.84 27.80 24.00 1.88 1.72 1.55 1.39 1.22 O O 41 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 40

R616_1-4.JDF 11.01 7.51 7.50 7.37 7.36 7.24 7.22 7.02 7.01 6.97 6.96 6.80 6.79 6.63 6.32 6.30 5.43 5.36 5.35 4.02 3.17 3.15 2.87 2.86 2.85 2.84 2.83 2.57 2.55 2.55 2.54 2.47 2.24 2.13 1.71 1.67 1.65 1.02 0.69 0.97 1.03 1.05 1.01 1.07 1.09 1.06 1.04 1.01 1.04 1.03 1.04 1.10 4.13 5.136.20 6.09 1.11 3.21 3.17 3.09 R616_13C-2.JDF DMSO-d6 141.79 135.94 132.96 131.96 127.71 121.28 119.71 119.33 118.62 118.40 118.24 118.08 111.23 111.15 109.06 102.81 60.29 59.63 57.04 45.22 45.10 39.85 39.68 39.51 39.35 39.18 39.01 36.43 31.43 28.44 27.35 23.69 22.48 22.27 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 41

R718_1-4.JDF CLOROFORM-d 8.46 7.67 7.65 7.50 7.48 7.27 7.19 7.15 7.15 7.14 7.14 6.96 6.95 6.77 6.49 6.48 5.47 5.46 5.44 4.05 3.12 3.12 3.11 3.03 3.03 3.02 3.01 3.00 2.80 2.79 2.40 2.37 2.17 1.80 1.77 1.71 1.11 0.81 0.91 1.02 1.00 3.11 1.06 1.00 0.97 2.00 1.00 5.15 4.21 6.05 6.21 1.081.06 3.02 3.12 3.10 R718_13C-3.JDF CLOROFORM-d 142.25 136.27 133.26 132.74 132.58 132.25 128.14 122.23 120.72 119.30 119.04 118.93 118.28 112.18 111.39 109.79 103.08 77.37 77.12 76.87 60.41 59.97 58.99 53.84 45.54 45.46 41.03 37.17 31.96 28.95 27.38 23.98 23.46 23.01 Dimethyl isoborreverine (6) CDCl 3, 125 Mz 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 42

R716TFA_1-4 (1).JDF 11.21 10.20 10.10 7.67 7.65 7.52 7.51 7.28 7.26 7.09 7.07 7.04 7.02 6.88 6.87 6.72 6.71 6.22 6.20 5.50 5.48 5.46 4.11 3.34 3.33 3.22 3.21 3.20 3.19 3.15 3.13 3.12 2.92 2.82 2.48 2.30 2.27 1.72 1.69 1.04 0.69 TFA salt of synthetic Dimethyl isoborreverine (6) 500 Mz, DMSO-d6 R716TFA_13C-6.JDF 142.86 133.86 132.13 131.78 131.32 128.77 128.08 126.93 121.70 120.16 118.92 118.55 118.50 118.10 111.32 108.96 98.99 57.13 56.55 42.06 39.87 39.69 39.62 39.53 39.36 39.19 39.03 38.86 36.26 31.37 28.19 27.41 23.50 19.35 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 43

Jeremy A. May et.al. JACS 2012 R616_1-4.JDF 11.01 7.51 7.50 7.37 7.36 7.24 7.22 7.02 7.01 6.97 6.96 6.80 6.79 6.63 6.32 6.30 5.43 5.36 5.35 4.02 3.17 3.15 2.87 2.86 2.85 2.84 2.83 2.57 2.55 2.55 2.47 2.46 2.24 2.13 1.71 1.67 1.65 1.02 0.69 Synthetic Dimethyl isoborreverine (6) 500 Mz, DMSO-d6 44

Jeremy A. May et.al. JACS 2012 MR Solvent: CDCl 3 R718_13C-3.JDF 142.25 136.27 133.26 132.74 132.58 132.25 128.14 122.23 120.72 119.30 119.04 118.93 118.29 112.18 111.39 109.79 103.08 77.38 77.12 76.87 60.42 59.97 59.00 53.84 45.54 45.46 41.04 37.17 31.97 28.95 27.39 23.98 23.46 23.01 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 45

ARD29_1-10.JDF 11.13 8.82 7.63 7.62 7.46 7.45 7.24 7.23 7.06 7.04 7.02 7.00 6.85 6.84 6.68 6.67 6.19 6.17 5.44 5.42 5.40 4.06 3.16 3.15 3.13 3.12 3.10 3.07 3.06 2.67 2.66 2.65 2.58 2.45 2.22 1.67 1.01 0.65 TFA salt of synthetic Isoborreverine (5) 500 Mz, DMSO-d6 0.85 1.01 1.02 1.05 1.08 1.11 1.06 0.99 1.00 0.97 0.93 0.95 8.35 3.14 3.06 2.05 1.01 3.35 3.13 3.05 ARD30_13C-3.JDF DMSO-d6 143.41 134.32 132.81 132.46 132.08 122.35 120.81 119.48 119.33 119.19 119.06 118.65 118.23 115.88 111.98 109.51 100.12 57.63 49.30 40.50 40.33 40.17 39.99 39.83 39.67 39.49 32.93 32.79 32.00 28.81 27.87 24.10 21.51 TFA salt of synthetic Isoborreverine (5) 125 Mz, DMSO-d6 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 46

ARD22_1-6.JDF 2O 11.05 7.57 7.55 7.42 7.40 7.22 7.21 7.03 7.01 6.98 6.97 6.81 6.80 6.64 6.28 6.27 5.44 5.40 5.38 4.04 3.61 3.15 3.14 3.12 2.93 2.90 2.86 2.74 2.46 2.42 1.66 1.01 0.68 Synthetic Isoborreverine (5) 500 Mz, DMSO-d 6 0.90 1.01 1.05 1.04 1.13 1.09 1.03 1.01 0.99 1.11 1.00 1.21 1.238.53 6.02 2.10 3.12 3.07 3.08 ARD24_13C-2.JDF DMSO-d6 142.98 136.72 133.95 132.76 128.53 122.10 120.53 120.02 119.46 119.16 118.93 111.96 109.78 103.04 57.81 52.70 40.75 40.59 40.41 40.25 40.09 39.91 39.75 36.34 36.29 32.22 29.18 28.12 24.44 Synthetic Isoborreverine (5) 125 Mz, DMSO-d 6 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 47

Jeremy A. May et. al. JACS 2012 DMSO d6 ARD29_1-10.JDF 11.13 8.82 7.63 7.62 7.46 7.45 7.24 7.23 7.06 7.04 7.02 7.00 6.85 6.84 6.68 6.67 6.19 6.17 5.44 5.42 5.40 4.06 3.16 3.15 3.13 3.12 3.10 3.07 3.06 2.67 2.66 2.65 2.58 2.45 2.22 1.67 1.01 0.65 48

Jeremy A. May et. Al. JACS 2012 DMSO d6 ARD24_13C-2.JDF 142.98 136.72 133.95 132.76 132.72 128.53 122.10 120.53 120.03 119.46 119.16 119.02 118.93 111.96 109.78 103.04 57.81 52.70 52.60 40.75 40.59 40.51 40.41 40.25 40.09 39.92 39.75 36.34 32.22 29.18 28.12 24.99 24.83 24.44 synthetic Isoborreverine (5) 125 Mz, DMSO-d6 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 49

CLOROFORM-d 7.70 7.69 7.68 7.68 7.52 7.50 7.27 7.14 7.13 6.98 6.96 6.94 6.77 6.75 6.46 6.44 5.47 5.45 4.06 3.15 3.12 3.11 3.07 3.05 3.04 3.03 3.01 3.00 2.47 2.39 2.21 2.17 1.79 1.75 1.70 1.10 0.81 Synthetic Isoborreverine (5) 400 Mz, CDCl 3 1.09 1.15 3.25 1.22 1.09 1.00 2.04 1.08 9.98 3.22 3.08 2.31 1.37 3.11 3.18 3.19 CLOROFORM-d 143.40 136.80 133.98 133.29 132.80 128.90 122.80 121.34 119.86 119.60 119.01 112.67 111.83 110.17 103.07 77.99 77.66 77.34 59.58 54.50 53.09 52.64 41.52 37.70 37.00 36.56 32.51 29.47 28.03 26.05 25.12 24.50 Synthetic Isoborreverine (5) 100 Mz, CDCl 3 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 50

R32PDIALDEYDE_1-4.JDF 2O 9.60 9.46 9.40 7.41 7.40 7.38 7.37 7.35 7.28 7.26 7.11 7.00 6.99 6.37 6.34 6.09 6.05 5.24 5.24 5.23 5.22 4.26 4.24 4.23 4.21 3.66 3.66 3.65 3.63 3.62 3.60 2.86 2.85 2.84 2.82 2.33 2.31 2.30 2.29 2.16 1.94 1.76 1.75 O 42a O 1.05 1.03 1.05 3.25 1.09 1.14 3.45 1.08 1.00 1.11 1.07 4.09 1.09 1.07 3.00 6.11 R3+2PDIALDEYDE_13C-1.JDF ACETOITRILE-d3 ACETOITRILE-d3 200.68 199.85 146.34 137.57 135.11 134.37 133.48 125.37 123.96 121.63 120.59 120.09 119.47 119.37 118.39 117.39 111.84 111.37 106.49 97.66 65.19 51.74 39.68 39.48 35.78 25.85 25.79 18.42 1.89 1.72 1.55 1.39 1.22 1.06 O 42a O 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 51

EPIFIALA_1-4.JDF 2O DMSO-d6 10.94 7.45 7.39 7.38 7.32 7.18 7.17 7.00 6.94 6.93 6.93 6.87 6.42 6.38 6.08 6.05 5.26 5.24 4.18 4.16 4.14 4.13 3.36 3.35 3.35 2.71 2.70 2.63 2.63 2.62 2.60 2.47 2.46 2.45 2.29 2.15 1.90 1.76 1.73 1.01 1.09 1.07 1.05 1.10 1.11 2.33 1.17 1.00 0.98 1.06 1.06 1.428.22 3.02 1.30 3.023.07 3.19 3.41 EPIFLIDA_13C-2.JDF DMSO-d6 142.97 136.39 132.70 132.43 131.87 131.01 128.08 125.13 122.06 119.98 118.52 118.41 118.37 116.49 112.56 110.65 110.09 103.65 63.37 60.74 52.45 40.01 39.85 39.67 39.51 39.34 39.17 39.01 35.60 35.48 29.22 25.52 25.10 23.44 17.97 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 52

EPIFLIDA_DEPT135-4.JDF DMSO-d6 130.76 124.88 121.82 119.72 118.26 118.12 118.05 116.24 110.40 109.85 52.20 52.10 50.55 39.84 39.68 39.51 39.35 39.18 35.35 35.23 34.17 25.27 24.85 23.18 23.13 Synthetic Flinderole A (1) 125 Mz, DMSO-d 6 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 53

Jeremy A. May et.al. JACS 2012 DMSO d6 EPIFIALA_1-4.JDF 10.94 7.45 7.39 7.38 7.32 7.19 7.17 7.00 6.95 6.94 6.93 6.87 6.42 6.38 6.08 6.05 5.26 5.24 4.18 4.16 4.14 3.36 3.35 3.35 3.31 2.71 2.70 2.67 2.64 2.63 2.62 2.60 2.46 2.46 2.29 2.15 1.90 1.76 1.73 Synthetic Flinderole A (1) 500 Mz, DMSO-d 6 54

11.14 8.90 8.84 8.78 7.58 7.57 7.55 7.53 7.42 7.25 7.24 7.08 7.04 7.03 7.02 6.99 6.98 6.57 6.54 6.51 5.32 5.30 4.33 4.32 4.30 4.28 3.06 3.04 2.99 2.95 2.63 2.62 2.61 2.57 2.56 2.55 2.51 2.51 2.30 1.96 1.85 1.80 11.5 11.0 10.5 10.0 9.5 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 55

143.62 136.41 133.10 132.44 132.21 132.07 130.88 127.63 124.91 122.40 120.32 118.82 118.62 118.24 116.43 110.83 110.15 109.21 100.28 63.27 50.62 48.82 39.97 39.80 39.72 39.64 39.47 39.30 39.14 38.96 32.38 32.30 25.40 24.61 20.32 20.23 18.00 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 56

R657_1-4.JDF 2O CLOROFORM-d Grease 9.69 9.69 9.68 9.66 9.65 9.65 8.25 7.50 7.30 7.29 7.27 7.26 7.23 7.13 7.08 7.07 7.07 6.73 6.69 6.38 6.34 5.22 5.20 4.32 4.30 4.29 4.27 3.83 3.66 2.74 2.72 2.71 2.70 2.42 2.40 2.39 2.38 1.82 1.78 1.77 1.62 1.26 O O 42b 1.02 1.03 1.08 2.19 2.12 1.16 3.48 1.011.10 1.06 1.15 2.13 2.16 1.05 1.13 3.34 3.20 3.15 11.5 11.0 10.5 10.0 9.5 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 0.5 0 R657_13C-2.JDF CLOROFORM-d Graese 199.87 198.61 144.28 136.27 134.44 133.60 133.00 132.80 124.14 123.79 120.98 120.40 119.48 118.63 118.40 117.80 110.83 110.04 105.91 96.55 77.26 77.00 76.75 63.27 51.72 39.41 38.90 35.35 29.69 25.69 22.91 18.27 O 42b O 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 57

R637_DEPT135-4.JDF Grease 199.90 198.63 O 133.60 124.14 123.80 120.99 120.41 119.48 118.64 118.41 117.81 110.84 110.05 51.72 39.41 38.90 35.36 29.69 25.69 22.91 42b O 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 RFLIDA_1-19.JDF DMSO-d6 11.03 7.50 7.48 7.24 7.24 7.22 7.06 6.94 6.94 6.93 6.92 6.71 6.59 6.56 5.27 5.26 4.36 4.34 4.33 4.31 2.86 2.72 2.71 2.67 2.66 2.64 2.51 2.50 2.50 2.32 2.28 1.83 1.75 1.71 1.08 1.09 1.14 1.151.15 1.23 3.97 1.01 1.09 1.09 1.14 2.05 8.23 3.65 3.58 3.23 3.22 3.41 58

REPIFLIDA_13C-3.JDF DMSO-d6 142.56 136.49 132.80 132.40 132.25 132.03 128.18 125.41 122.17 119.79 118.53 118.38 118.23 117.94 113.04 110.71 109.77 103.74 62.72 52.70 52.64 51.01 40.02 39.84 39.68 39.51 39.35 39.18 39.01 35.79 34.73 25.55 23.77 23.65 22.84 18.03 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 RFLIDA_DEPT135-4.JDF DMSO-d6 132.14 125.15 121.91 119.54 118.28 118.12 117.96 117.70 110.46 109.50 52.47 50.75 39.68 39.51 39.34 35.56 34.48 25.30 23.54 23.42 22.57 17.77 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 59

Jeremy A. May et.al. JACS 2012 RFLIDA_1-19.JDF 11.03 7.50 7.48 7.24 7.24 7.22 7.06 6.94 6.93 6.92 6.75 6.71 6.59 6.56 5.27 5.26 4.36 4.34 4.33 4.31 2.86 2.72 2.71 2.67 2.66 2.51 2.50 2.50 2.49 2.32 2.28 1.83 1.75 1.71 Synthetic Desmethyl Flinderole C 500 Mz, DMSO-d6 60

ARD10_1-4.JDF 7.99 7.97 7.84 7.83 7.49 7.47 7.45 7.38 7.37 7.30 7.22 7.21 4.96 4.09 4.08 3.43 3.42 2.85 1.20 1.00 2.00 2.09 3.02 1.11 1.04 1.01 2.08 2.06 2.09 3.12 ARD1013_13C-1.JDF CLOROFORM-d 156.51 137.85 135.13 133.62 130.58 129.07 126.50 124.76 123.23 123.14 119.98 119.34 113.58 77.25 77.00 76.74 60.61 40.07 25.41 14.48 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 61

ARD1013_DEPT135-3.JDF 133.88 129.34 126.77 125.03 123.41 119.61 113.84 60.89 40.33 25.67 14.75 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD31_1-4.JDF 8.91 7.62 7.60 7.55 7.45 7.43 7.41 7.31 7.29 7.28 7.11 7.09 6.30 4.14 4.13 4.11 4.10 3.89 3.87 3.85 2.83 2.23 2.20 2.19 2.17 1.99 1.98 1.97 1.96 1.25 1.00 3.09 1.15 3.22 2.12 1.07 2.071.08 1.04 1.111.04 3.35 62

ARD31_13C-1.JDF CLOROFORM-d 194.36 153.74 142.26 137.08 133.24 129.82 128.81 126.85 125.70 124.39 79.31 77.26 77.00 76.74 61.78 44.82 33.29 14.17 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD41_1-4.JDF 7.62 7.61 7.31 7.29 7.26 7.25 7.23 7.22 7.20 7.10 6.98 6.96 6.53 6.50 5.88 4.89 4.15 4.13 4.05 4.04 4.03 4.02 4.02 4.01 3.80 3.79 2.80 2.79 2.78 2.07 2.05 2.05 2.03 2.02 1.29 1.26 1.23 1.20 1.20 1.19 1.18 1.17 1.12 2.01 2.16 2.01 1.02 1.00 1.01 0.94 0.97 2.10 2.07 1.01 1.00 2.13 3.03 3.66 63

ARD38_13C-3.JDF CLOROFORM-d 165.21 154.00 146.66 142.05 137.87 133.09 132.37 129.37 128.71 127.12 125.71 124.58 121.97 118.47 83.23 77.25 77.00 76.74 61.84 60.31 45.55 14.35 14.05 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD38_135DEPT-4.JDF 146.90 133.34 129.61 128.95 127.37 125.96 124.83 122.20 118.70 83.47 62.09 60.56 45.79 14.60 14.29 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 64

ARD42_1-8.JDF CLOROFORM-d 7.65 7.63 7.49 7.43 7.43 7.42 7.41 7.39 7.38 7.07 7.02 7.02 5.96 5.38 4.16 4.15 4.15 4.14 4.13 4.11 3.86 3.84 3.84 3.82 2.86 2.85 2.84 2.14 2.12 2.11 2.10 2.09 2.07 2.06 2.05 1.25 1.24 1.23 1.13 1.11 1.33 1.36 2.13 1.55 2.14 1.05 1.02 1.01 0.95 2.07 2.021.01 1.02 2.39 3.42 3.22 3.02 ARD42_13C-2.JDF CLOROFORM-d 154.24 141.63 138.96 134.41 132.84 131.91 131.84 128.81 128.63 128.38 128.29 127.43 127.03 124.32 116.58 83.87 77.26 77.00 76.75 70.10 61.65 45.54 29.52 29.49 14.32 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 65

ARD42_135DEPT-3.JDF 139.22 133.09 132.17 132.09 129.07 128.89 128.64 128.54 127.68 125.21 124.58 116.80 84.13 61.91 45.79 29.77 14.58 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD48_1-5.JDF 7.72 7.67 7.37 7.35 7.30 7.28 7.26 7.25 7.13 7.11 7.04 7.02 5.92 5.50 5.46 5.33 5.30 4.87 4.65 4.21 4.20 4.20 4.19 4.18 4.18 3.86 3.85 3.84 3.83 2.87 2.86 2.85 2.83 2.81 2.81 2.15 2.13 2.11 2.11 2.09 1.61 1.39 1.33 1.27 CO 2 Et SO 2 Ph 49 3.03 1.04 3.15 1.04 1.00 0.91 1.01 1.02 1.001.00 2.00 1.00 1.24 2.08 3.183.08 66

ARD20_13C-4.JDF CLOROFORM-d 154.12 141.74 140.40 138.09 134.10 133.36 133.23 130.17 128.68 128.57 128.44 127.04 125.18 124.59 117.61 84.04 77.26 77.00 76.75 61.60 45.55 18.25 14.32 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD20_DEPT135-5.JDF 133.67 133.53 130.47 128.99 128.88 128.74 127.34 125.48 124.90 117.92 84.33 61.91 45.86 18.55 14.63 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 67

ARD50_1-4.JDF 7.08 7.06 7.05 7.04 6.75 6.75 6.73 6.72 6.72 6.62 6.07 6.04 5.93 5.89 5.42 5.31 5.17 4.91 4.85 4.85 4.14 4.12 4.11 4.09 4.07 4.06 4.05 3.66 3.64 2.94 2.93 2.91 2.29 2.28 2.27 2.26 2.25 2.24 1.78 1.29 1.28 1.26 1.19 1.18 1.17 2.09 1.02 1.00 1.02 1.03 1.05 1.05 2.09 2.15 1.06 1.07 2.28 3.14 3.50 ARD50_13C-2.JDF ACETOITRILE-d3 ACETOITRILE-d3 155.67 154.98 150.82 150.75 142.64 133.38 133.27 132.57 131.44 129.49 125.02 119.73 119.70 118.28 117.11 110.55 110.36 82.38 81.88 61.97 61.77 60.47 59.43 46.94 46.74 36.41 36.14 18.89 15.15 1.88 1.71 1.55 1.39 1.22 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 68

ARD50A_DEPT135-3.JDF 141.73 132.46 132.36 131.66 128.57 124.12 118.80 116.20 109.64 109.45 81.47 80.98 61.07 60.88 46.04 45.84 35.50 35.22 17.98 14.24 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD34_1-4.JDF CLOROFORM-d grease 7.27 7.06 7.05 7.04 6.79 6.77 6.76 6.64 6.62 6.13 6.10 5.96 5.93 4.92 4.89 4.57 2.79 2.78 2.78 2.77 2.68 2.67 2.46 2.36 2.34 2.34 2.10 2.08 1.84 1.27 2.141.10 1.02 1.00 1.04 2.33 1.05 1.18 1.06 3.35 1.34 1.15 3.41 69

ARD44_13C-1.JDF CLOROFORM-d 150.09 141.61 134.95 133.69 131.26 127.87 124.73 119.01 116.05 109.37 89.10 77.25 77.00 76.74 59.75 52.36 39.76 36.87 18.71 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ARD44_DEPT135-3.JDF 135.06 131.39 128.00 124.84 119.13 116.17 109.49 89.22 52.48 39.88 36.99 18.83 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 70

ARD12_1-4.JDF CLOROFORM-d DCM 7.27 7.10 7.08 7.07 7.04 7.02 6.78 6.77 6.75 6.63 6.62 6.61 5.87 5.87 5.84 5.84 5.58 5.55 5.18 5.15 4.21 4.20 4.19 4.14 4.12 4.11 4.09 3.67 3.66 3.66 3.08 3.07 2.27 2.26 2.26 2.25 2.24 2.23 1.33 1.32 1.31 1.27 1.26 1.25 1.24 1.22 1.031.01 1.02 1.00 1.01 1.00 1.07 2.06 1.05 1.04 2.06 1.12 9.76 ARD121_13C-2.JDF CLOROFORM-d 155.07 154.14 149.21 148.88 137.71 130.43 130.32 128.47 128.41 128.34 123.85 119.34 119.04 109.75 109.60 81.34 80.87 77.26 77.00 76.75 70.44 70.42 61.33 61.07 59.01 57.94 46.02 45.72 35.53 35.30 29.68 29.63 14.76 14.58 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 71

R637B_1-4.JDF CLOROFORM-d 7.27 7.05 7.03 7.02 7.00 6.99 6.75 6.74 6.72 6.60 6.59 5.94 5.91 5.60 5.57 4.51 4.24 2.74 2.73 2.73 2.72 2.63 2.62 2.61 2.42 2.29 2.28 2.26 2.03 1.28 1.27 1.021.00 1.02 1.00 1.02 1.00 1.04 0.97 1.13 1.18 3.31 1.51 1.13 6.46 R637B_13C-2.JDF CLOROFORM-d 150.07 136.48 133.69 131.61 127.74 124.47 118.82 109.17 88.63 77.25 77.00 76.74 70.40 59.10 52.24 39.54 36.72 29.75 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 72

R637B_DEPT135-3.JDF 136.67 131.79 127.93 124.66 119.01 109.36 88.81 52.42 39.72 36.91 29.93 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 73