A Concise Approach to the Dalesconol Skeleton

A Concise Approach to the Dalesconol Skeleton Yukai Fan, a Pengju Feng, a Mao Liu, a Hongjie Pan, a and Yian Shi* a,b a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. b Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523 Supporting Information S-1

General Procedures. All commercially available reagents were used without further purification unless otherwise stated. All dry solvents were freshly distilled under nitrogen from appropriate drying agents. Tetrahydrofuran was distilled from sodium-benzophenone. CH 2 Cl 2 was distilled from CaH 2, and N,N-dimethylformamide was distilled from MgSO 4. Column chromatography was performed on silica gel (200-300 mesh). 1 H NMR spectra were recorded on a 400 MHz NMR spectrometer and 13 C NMR spectra were recorded on a 100 MHz NMR spectrometer. IR spectra were recorded on a FT-IR spectrometer. Melting points were uncorrected. Synthesis of Compound 11 O 2 S O KOH OH OH MeI (1.1 equiv) K 2 CO 3 (1.1 equiv) OMe OH NBS (1.0 equiv) CH 3 CN, rt OMe OH 10 260 o C 73% acetone, rt 95% 97% 11 Br 1,8-Naphthalenesultone 10 (23.5 g, 114.0 mmol), KOH (205.0 g, 3660.7 mmol), and a magnetic stirring bar were placed in a flask (the glass flask could be damaged if its quality is poor, and a stainless steel pot is recommended). The mixture was heated under nitrogen in an oil bath (260 o C). The resulting dark solution was stirred at this temperature for 1 h (KOH melted at about 250 o C). Upon cooling to room temperature under nitrogen, the reaction mixture was acidified with 1N HCl to ph about 1.0 and extracted with EtOAc (5x200 ml). The combined organic phase was dried over MgSO 4, filtered, concentrated, and purified with flash chromatography (petroleum ether:ethyl acetate = 15:1 to 5:1) to give naphthalene-1,8-diol as white solid (13.27 g, 73%). R f = 0.30 (silica gel, PE:EtOAc = 5:1); mp. 135-136 o C; IR (film): 3146 (br), 1611, 1408, 1277, 1261, 1031, 814, 752 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.84 (s, 2H), 7.38 (d, J = 8.0 Hz, 2H), 7.29 (t, J = 7.6 Hz, 2H), 6.81 (d, J = 7.6 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 152.8, 137.2, 126.9, 120.8, 114.7, 109.6. (a) Erdmann, H. Justus Liehigs Ann. Chem. 1888, 247, 345. (b) Parker, K. A.; Iqbal, T. J. S-2

Org. Chem. 1980, 45, 1149. (c) Andersen, N. G.; Maddaford, S. P.; Keay, B. A. J. Org. Chem. 1996, 61, 9556. To a suspension of naphthalene-1,8-diol (33.41 g, 208.80 mmol) and K 2 CO 3 (28.82 g, 208.80 mmol) in acetone (300 ml) was added MeI (32.62 g, 229.70 mmol). After the reaction mixture was stirred at 18 o C for 9 h, another batch of K 2 CO 3 (2.80 g, 20.88 mmol) was added. Upon stirring at 18 o C for 10 h, the reaction mixture was concentrated, acidified with 1N HCl aqueous solution, extracted with Et 2 O (5x100 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate = 10:1 to 5:1) to afford 8-methoxynaphthalen-1-ol as white solid (34.41 g, 95%). R f = 0.52 (silica gel, PE:EtOAc = 5:1); mp. 47-49 o C; IR (film): 3404 (br), 3057, 1631, 1583, 1455, 1307, 1261, 1075, 965, 815, 755, 674 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 9.32 (s, 1H), 7.42 (d, J = 8.4 Hz, 1H), 7.38-7.29 (m, 3H), 6.89 (d, J = 7.2 Hz, 1H), 6.78 (d, J = 7.6 Hz, 1H), 4.06 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 156.4, 154.7, 137.0, 127.9, 125.8, 122.1, 119.1, 115.3, 110.6, 104.1, 56.3. To a solution of 8-methoxynaphthalen-1-ol (12.43 g, 71.44 mmol) in CH 3 CN (250 ml) was added NBS (12.79 g, 71.44 mmol) in a single portion. The resulting dark solution was stirred for 23 h, concentrated, and purified by flash column chromatography (petroleum ether:ethyl acetate = 15:1 to 7:1) to give 4-bromo-8-methoxynaphthalen-1-ol (11) as white solid (17.55 g, 97%). R f = 0.43 (silica gel, petroleum ether:ethyl acetate = 5:1); mp. 51-52 0 C; IR (film): 3333, 1625, 1610, 1394, 1277, 1264, 1084, 982, 818, 748 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 9.45 (s, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.42 (t, J = 8.4 Hz, 1H), 6.82 ( d, J = 7.6 Hz, 1H), 6.76 (d, J = 8.4 Hz, 1H), 4.04 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 156.3, 154.8, 134.4, 131.8, 127.2, 121.4, 116.3, 111.4, 111.3, 105.0, 56.5. (a) Carreño, M. C.; García Ruano, J. L.; Sanz, G.; Toledo, M. A.; Urbano, A. Synlett. 1997, 1241. (b) Snyder, S. A.; Sherwood, T. C.; Ross, A. G. Angew. Chem. Int. Ed. 2010, 49, 5146. S-3

Synthesis of Compound 8 OMe OH Br 11 NaH (1.3 equiv) MOMCl (1.5 equiv) OMe OMOM n-buli (1.2 equiv) DMF (4.0 equiv) DMF, 97% THF, 83% Br OMe OMOM OMe OMOM NBS (1.05 equiv) DMF, 87% CHO Br CHO 12 8 To a solution of compound 11 (10.13 g, 40.0 mmol) in DMF (100 ml) was added NaH (60% in mineral oil) (2.10 g, 52.5 mmol) at 0 o C. After the reaction mixture was stirred at 0 o C for 80 min, MOMCl (4.83 g, 60.0 mmol) was added dropwise. Upon stirring at 0 o C for 6 h, the reaction mixture was quenched with saturated NH 4 Cl aqueous soluiton (150 ml), diluted with water (100 ml), extracted with Et 2 O (3x150 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate = 10:1 to 5:1) to give the product as white solid (11.55 g, 97%). R f = 0.43 (silica gel, petroleum ether/ethyl acetate = 5:1); mp. 65-66 o C; IR (film): 1614, 1589, 1576, 1462, 1398, 1376, 1269, 1231, 1148, 1080, 996, 950, 819, 749 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (d, J = 8.8 Hz, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.48 (t, J = 8.4 Hz, 1H), 6.96-6.93 (m, 2H), 5.25 (s, 2H), 3.97 (s, 3H), 3.59 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 157.2, 154.2, 135.2, 130.6, 127.8, 120.5, 120.1, 116.1, 113.9, 107.4, 97.1, 56.7, 56.6. Snyder, S. A.; Sherwood, T. C.; Ross, A. G. Angew. Chem. Int. Ed. 2010, 49, 5146. To a solution of the above bromide (3.52 g, 11.85 mmol) in anhydrous THF (40 ml) under nitrogen at -78 o C was slowly added n-buli solution in hexane (2.5 M) (5.68 ml, 14.2 mmol). After the reaction mixture was stirred at -78 o C for 10 min, anhydrous DMF (3.459 g, 47.38 mmol) was added. Upon stirring at -78 o C for 25 min, the reaction mixture was warmed to rt, quenched with saturated NH 4 Cl aqueous solution (20 ml), diluted with water (100 ml), extracted with Et 2 O (5x40 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate = 8:1 to 3:1) give aldehyde 12 as white solid (2.406 g, 83%). R f = 0.45 (silica gel, petroleum ether:ethyl acetate = 4:1); S-4

mp. 84 o C; IR (film): 2708, 2696, 1683, 1611, 1581, 1465, 1279, 1150, 1029, 952, 828, 811, 764 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 10.20 (s, 1H), 8.95 (d, J = 8.4 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.56 (t, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 6.96 (d, J = 8.0 Hz, 1H), 5.39 (s, 2H), 3.96 (s, 3H), 3.59 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 192.3, 160.3, 157.7, 139.5, 135.2, 129.9, 125.5, 117.9, 117.2, 108.8, 107.8, 95.4, 56.8, 56.5. Snyder, S. A.; Sherwood, T. C.; Ross, A. G. Angew. Chem. Int. Ed. 2010, 49, 5146. To a solution of aldehyde 12 (2.599 g, 10.57 mmol) in DMF (60 ml) was added at rt portionwise NBS (1.986 g, 11.10 mmol). The reaction mixture was stirred at rt overnight, diluted with water (500 ml), extracted with EtOAc/Et 2 O (1:1) (5x100 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate:ch 2 Cl 2 = 5:1:0 to 2:1:1) to give product 8 as white solid (2.998 g, 87%). R f = 0.58 (silica gel, petroleum ether/ethyl acetate = 3:1); mp. 129-131 o C; IR (film): 1665, 1582, 1570, 1407, 1380, 1357, 1280, 1171, 1128, 1108, 953, 939, 812 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 11.13 (s, 1H), 7.85 (d, J = 8.4 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.77 (d, J = 8.4 Hz, 1H), 5.33 (s, 2H), 3.96 (s, 3H), 3.58 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 191.2, 158.6, 158.0, 134.5, 134.2, 131.8, 129.8, 120.3, 110.6, 109.1, 107.9, 95.8, 56.84, 56.78; HRMS Calcd for C 14 H 13 O 79 4 Br (M + ): 323.9997; Found: 324.0000; HRMS Calcd for C 14 H 13 O 81 4 Br (M + ): 325.9977; Found: 325.9980. Mallory, F. B.; Mallory, C. W.; Butler, K. E.; Lewis, M. B.; Xia, A. Q.; Luzik, Jr., E. D.; Fredenburgh, L. E.; Ramanjulu, M. M.; Van, Q. N.; Francl, M. M.; Freed, D. A.; Wray, C. C.; Hann, C.; Nerz-Stormes, M.; Carroll, P. J.; Chirlian, L. E. J. Am. Chem. Soc. 2000, 122, 4108. Synthesis of Compound 9 OMe OTIPS OMe OH TIPSCl (1.1 equiv) imidazole (5.0 equiv) OMe OTIPS pinacolborane (1.5 equiv) Pd(PPh 3 ) 4 (5 mol%) Br DMAP (0.1 equiv) DMF, 85% Br Et 3 N (3.0 equiv) 1,4-dioxane, 85% B O O 11 13 9 S-5

To a solution of 2-bromo-1-hydroxy-8-methoxynaphthalene (11) (2.53 g, 10.00 mmol), imidazole (3.40 g, 50.00 mmol), and DMAP (0.122 g, 1.00 mmol) in DMF (30 ml) was added TIPSCl (2.12 g, 11.00 mmol). Upon stirring at 50 o C for 14 h, the reaction mixture was then poured into saturated NH 4 Cl aqueous solution (30 ml). After water (200 ml) was added, the mixture was extracted with Et 2 O (5x50 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate = 100:0 to 50:1) to give compound 13 as colorless crystal (3.47 g, 85%). R f = 0.93 (silica gel, petroleum ether:ethyl acetate = 50:1); mp. 60-64 ; IR (film): 1584, 1459, 1400, 1374, 1312, 1279, 1245, 1098, 1052, 1015, 993, 882, 850, 817, 791, 773, 749, 687 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.78 (d, J = 8.4 Hz, 1H), 7.57 (d, J = 8.0 Hz, 1H), 7.44 (t, J = 8.0 Hz, 1H), 6.85 (d, J = 8.0 Hz, 1H), 6.67 (d, J = 8.4 Hz, 1H), 3.90 (s, 3H), 1.40-1.30 (m, 3H), 1.14 (d, J = 7.6 Hz, 18H); 13 C NMR (100 MHz, CDCl 3 ) δ 157.8, 153.6, 135.3, 130.6, 127.6, 120.8, 119.9, 115.0, 113.5, 105.9, 55.6, 18.2, 13.6. HRMS Calcd for C 20 H 29 O 2 Si 79 Br (M + ): 408.1120; Found: 408.1123; HRMS Calcd for C 20 H 29 O 2 Si 81 Br (M + ): 410.1100; Found: 410.1106. (a) Landi Jr., J. J.; Ramig, K. Synth. Commun. 1991, 21, 167. (b) Couladouros, E; Strongilos, A.T. Tetrahedron Lett., 2000, 41, 535. A two-necked flask containing compound 13 (4.09 g, 10.0 mmol) and Pd(PPh 3 ) 4 (0.58 g, 0.50 mmol) was evacuated and refilled with nitrogen for 5 times. Anhydrous 1,4-dioxane (20 ml) was then added, followed by addition of Et 3 N (3.03 g, 30.0 mmol) and pinacolborane (1.92 g, 15.0 mmol). Upon sitrring at 90 o C for 18 h, the reaction mixture was poured into water (200 ml), extracted with EtOAc (5x50 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate = 100:0 to 50:1) to give product 9 as colorless syrup (3.88 g, 85%), which became colorless solid upon standing at rt. R f = 0.83 (silica gel, petroleum ether:ethyl acetate = 50:1); mp. 69-71 ; IR (film): 1580, 1463, 1344, 1326, 1291, 1272, 1145, 1104, 1055, 1014, 855, 750 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 8.41 (d, J = 8.4 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), S-6

7.42 (t, J = 8.0 Hz, 1H), 6.85 (d, J = 8.0 Hz, 1H), 6.81 (d, J = 7.6 Hz, 1H), 3.91 (s, 3H), 1.46-1.39 (m, 15H), 1.19 (d, J = 7.2 Hz, 18H); 13 C NMR (100 MHz, CDCl 3 ) δ 157.7, 156.7, 141.9, 137.2, 126.6, 121.0, 119.5, 114.2, 104.9, 83.5, 55.3, 25.1, 18.2, 13.6; HRMS Calcd for C 26 H 41 BO 4 Si (M + ): 456.2867; Found: 456.2873. (a) Thompson, A. L. S.; Kabalka, G. W.; Akula, M. R.; Huffman, J. W. Synthesis, 2005, 4, 547. (b) Babudri, F.; Cardone, A. C.; Cioffi, T.; Farinola, G. M.; Naso, F.; Ragnib, R. Synthesis, 2006, 8, 1325. Synthesis of Compound 6 O Br HC(OMe) 3 MeOH, TsOH 97% H 3 CO OCH 3 6 Br To a solution of o-bromoacetophenone (4.62 g, 23.22 mmol) in MeOH (25 ml) were added HC(OMe) 3 (5.0 ml, 45.7 mmol) and p-tsoh (0.076 g, 0.44 mmol). Upon stirring at 65 o C overnight, the reaction mixture was neutralized with 1 % KOH solution in MeOH (4 ml), concentrated, and distilled under reduced pressure to give compound 6 as colorless oil (5.503 g, 97%). R f = 0.70 (silica gel, petroleum ether:ethyl acetate = 5:1); IR (film): 1462, 1426, 1371, 1280, 1245, 1187, 1151, 1097, 1054, 1037, 1021, 879, 758 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (d, J = 8.0 Hz, 1H), 7.60 (d, J = 7.6 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 7.12 (td, J = 7.6, 1.6 Hz, 1H), 3.20, (s, 6H), 1.68 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 140.7, 135.0, 130.1, 129.4, 127.4, 120.7, 101.4, 48.9, 23.1. Wang, S.; Morrow, G. W.; Swenton, J. S. J. Org. Chem. 1989, 54, 5364. S-7

Synthesis of Compound 7 OMe OTIPS OMe OTIPS Br CHO + OMe OMOM B O O Pd(PPh 3 ) 4 (10 mol%) Na 2 CO 3 1,4-dioxane, 53% CHO 8 9 OMe 7 OMOM A flask charged with 8 (0.100 g, 0.31 mmol), 9 (0.170 g, 0.37 mmol), and Pd(PPh 3 ) 4 (0.036 g, 0.031 mmol) was evacuated and refilled with nitrogen for 3 times. 1,4-Dioxane (1.2 ml) was then added, followed by saturated Na 2 CO 3 aqueous solution (0.25 ml). Upon stirring at 70 o C overnight, the reaction mixture was quenched with saturated NH 4 Cl aqueous solution (2 ml), diluted with water (10 ml), extracted with Et 2 O (5x3 ml), dried over MgSO 4, filtered, concentrated, and purified by flash chromatography (petroleum ether:ethyl acetate = 10:1 to 5:1) to give compound 7 as yellow solid (0.094 g, 53%). R f = 0.62 (silica gel, petroleum ether:ethyl acetate = 3:1); mp. 109-113 o C; IR (film): 2866, 1677, 1580, 1461, 1377, 1273, 1074, 1009, 963, 817, 688 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 9.16 (s, 1H), 7.77 (d, J = 8.4 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.24-7.22 (m, 2H), 7.14 (d, J = 8.0 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 7.01 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.80 (t, J = 4.4 Hz, 1H), 5.39 (s, 2H), 4.04 (s, 3H), 3.92 (s, 3H), 3.64 (s, 3H), 1.46-1.38 (m, 3H), 1.19 (d, J = 7.2 Hz, 18H); 13 C NMR (100 MHz, CDCl 3 ) δ 190.8, 158.8, 158.0, 157.4, 153.8, 136.3, 133.1, 132.6, 130.4, 129.9, 129.4, 127.0, 120.2, 119.0, 118.6, 114.6, 110.5, 106.9, 105.5, 96.0, 56.8, 56.7, 55.4, 18.3, 13.6; HRMS Calcd for C 34 H 42 O 6 Si (M + ): 574.2751; Found: 574.2759. Lin, S.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2002, 41, 512. S-8

Synthesis of Compounds 4a and 4b H 3 CO OCH 3 OMe OTIPS CHO OMe OMOM 7 Br 6 n-buli Silica gel 86% (4a/4b =1.14/1) MeO O O OMe OMOM 4a + MeO O O OMe OMOM 4b To a solution of compound 6 (0.539 g, 2.20 mmol) in anhydrous THF (8 ml) at 20 o C under nitrogen was added dropwise n-buli solution in THF (2.5 M) (0.8 ml, 2.0 mmol). After the reaction mixture was stirred for 15 min, a solution of aldehyde 7 (0.574 g, 1.0 mmol) in THF (8 ml) was added. Upon stirring at 20 o C for 10 min, the reaction mixture was quenched with saturated NH 4 Cl (20 ml) aqueous solution, extracted with EtOAc (5x15 ml), dried over MgSO 4, filtered, concentrated, and then dissolved in 30 ml of CH 2 Cl 2, followed by addition of silica gel (200-300 mesh) (9 ml). The resulting slurry was stirred at 20 o C for 3 h and then at 40 o C for 3 h. Upon concentration, the solid residue was loaded onto the slica gel column and eluted with petroleum ether-ethyl acetate (3:1 to 3:2) to give compound compound 4a (0.205 g), 4b (0.188 g), and a mixture of 4a and 4b (0.0546 g) (86% combined yield, with the ratio of 4a to 4b as 1.14 : 1). 4a, White solid; R f = 0.31 (silica gel, petroleum ether:ethyl acetate = 1:2); mp. 206 o C; IR (film): 2836, 1680, 1661, 1594, 1466, 1456, 1432, 1260, 1063, 972, 913, 742 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.52 (d, J = 7.2 Hz, 1H), 7.34 (t, J = 8.0 Hz, 1H), 7.28-7.24 (m, 2H), 7.19 (d, J = 7.6 Hz, 1H), 7.14 (d, J = 7.6 Hz, 1H), 7.03 (d, J = 7.2 Hz, 1H), 6.88 (d, J = 8.4 Hz, 1H), 6.78-6.72 (m, 2H), 6.65 (d, J = 8.0 Hz, 1H), 6.38 (s, 1 H), 6.21 (d, J = 10.4 Hz, 1H), 5.89 (d, J = 10.4 Hz, 1H), 5.34 (s, 2H), 3.95 (s, 6H), 3.64 (s, 3H), 2.17 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 202.1, 185.0, 159.9, 155.4, 152.6, 152.3, 147.6, 141.9, 139.6, 139.3, 139.1, 138.8, 134.1, 131.2, 130.8, 129.1, 127.8, 127.2, 122.5, 121.4, 120.9, 116.9, S-9

115.5, 110.2, 108.3, 97.2, 61.3, 58.6, 56.7, 56.6, 56.4, 29.6; HRMS Calcd for C 33 H 28 O 6 (M + ): 520.1886; Found: 520.1892. 4b, White solid; R f = 0.33 (silica gel, petroleum ether:ethyl acetate = 1:2); mp. 209-210 o C; IR (film): 2836, 1684, 1660, 1593, 1466, 1455, 1432, 1260, 1169, 1063, 971, 760, 733 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.42 (d, J = 7.2 Hz, 1H), 7.17 (d, J = 7.6 Hz, 1H), 7.12-7.01 (m, 3H), 6.98-6.84 (m, 5H), 6.62-6.59 (m, 2H), 6.37 (d, J = 9.6 Hz, 1H), 5.88 (d, J = 8.0 Hz, 1H), 5.36 (s, 2H), 4.00 (s, 3H), 3.78 (s, 3H), 3.66 (s, 3H), 2.48 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 203.3, 185.0, 159.7, 155.5, 152.1, 150.3, 148.1, 142.6, 139.2, 138.9, 138.1, 137.0, 132.1, 131.4, 130.5, 129.4, 129.0, 126.9, 122.6, 122.5, 122.0, 121.4, 116.7, 115.3, 110.3, 108.3, 97.2, 60.7, 56.7, 56.6, 56.4, 30.0; HRMS Calcd for C 33 H 28 O 6 (M + ): 520.1886; Found: 520.1891. Synthesis of Compound 3 MeO O O LiHMDS (2.0 equiv) HCl (29.0 equiv) DDQ (1.0 equiv) THF, 85% from 4b MeO OMe O O OMe OMOM 4b O 3 To a solution of compound 4b (0.0428 g, 0.0823 mmol) in anhydrous THF (2 ml) at rt under nitrogen was added dropwise LiHMDS solution in THF (1.0 M) (0.165 ml, 0.165 mmol). The reaction mixture was stirred at rt until the reaction was completed as judged by TLC (about 30 min). At this point, concentrated HCl (12 N) (0.2 ml, 2.4 mmol) was added, followed addition of THF (2 ml). The reaction mixture was stirred at rt until the deprotection was completed as judged by TLC (about 40 min). DDQ (0.0187 g, 0.0823 mmol) and water (3 ml) were then added. Upon stirring at rt for 50 min (the reaction was completed as judged by TLC), the reaction mixture was diluted with water (20 ml), extracted with EtOAc (5x5 ml ), dried over MgSO 4, filtered, concentrated, and purified by preparative thin layer chromatography (petroleum ether:ethyl acetate = 1:4) to give compound 3 as S-10

orange solid (0.0332 g, yield 85%). R f = 0.36 (silica gel, ethyl acetate); IR (film): 1692, 1638, 1590, 1466, 1275, 1260, 764, 750 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.98 (d, J = 7.6 Hz, 1H), 7.60 (t, J = 7.2 Hz, 1H), 7.49-7.40 (m, 3H), 7.26 (d, J = 8.4 Hz, 1H), 7.15 (t, J = 8.0 Hz, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.75 (d, J = 8.4 Hz, 1H), 6.69 (d, J = 9.6 Hz, 1H), 6.23 (d, J = 8.0 Hz, 1H), 3.98 (s, 3H), 3.85 (s, 3H), 3.22-3.18 (m, 1H), 3.06-2.89 (m, 3H), 2.70 (dd, J = 14.4 Hz, 9.2 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 199.2, 195.8, 184.1, 159.2, 159.0, 158.0, 145.8, 143.3, 142.6, 136.6, 136.0, 134.8, 134.7, 134.2, 133.2, 131.4, 130.3, 129.8, 129.4, 127.3, 123.4, 119.5, 117.2, 111.1, 110.9, 64.1, 56.6, 56.3, 48.1, 45.2, 36.4; HRMS Calcd for C 31 H 22 O 5 (M + ): 474.1467; Found: 474.1475. S-11

The X-ray structure of compound 4a S-12

Table 1. Crystal data and structure refinement for mx997. Identification code mx997 Empirical formula C33 H28 O6 Formula weight 520.55 Temperature 173(2) K Wavelength 0.71073 A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 7.7247(15) A alpha = 84.359(6) deg. b = 14.258(3) A beta = 87.427(7) deg. c = 22.761(5) A gamma = 87.679(6) deg. Volume 2490.6(9) A^3 Z, Calculated density 4, 1.388 Mg/m^3 Absorption coefficient 0.095 mm^-1 F(000) 1096 Crystal size 0.24 x 0.20 x 0.12 mm Theta range for data collection 0.90 to 25.50 deg. Limiting indices -9<=h<=9, -17<=k<=17, -27<=l<=27 Reflections collected / unique 22325 / 9237 [R(int) = 0.0627] Completeness to theta = 25.50 99.5 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9887 and 0.9775 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 9237 / 9 / 731 Goodness-of-fit on F^2 1.159 Final R indices [I>2sigma(I)] R1 = 0.0825, wr2 = 0.1774 R indices (all data) R1 = 0.0980, wr2 = 0.1859 Largest diff. peak and hole 0.314 and -0.379 e.a^-3 S-13

Table 2. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for mx997. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) O(1) 7590(4) 8947(2) -1190(1) 53(1) O(2) 3028(4) 8134(2) -1838(1) 52(1) O(3) 1694(4) 9629(2) -1367(1) 61(1) O(4) 4821(3) 5332(2) 2066(1) 33(1) O(5) 8137(3) 5951(2) 2163(1) 28(1) O(6) 8400(4) 7189(2) 2750(1) 50(1) O(7) 2869(4) 5961(2) 6039(1) 42(1) O(8) -1697(4) 6646(2) 6779(1) 44(1) O(9) -3041(3) 5318(2) 6226(1) 40(1) O(10) 238(3) 9906(2) 2948(1) 41(1) O(11) 3559(3) 9280(2) 2791(1) 37(1) O(12) 4395(5) 8202(2) 2126(1) 69(1) C(1) 7321(4) 7465(2) -218(1) 22(1) C(2) 5293(4) 7200(2) -257(1) 23(1) C(3) 4944(4) 6628(2) 338(1) 23(1) C(4) 6354(4) 6662(2) 707(1) 22(1) C(5) 7740(4) 7157(2) 419(1) 22(1) C(6) 8507(4) 7001(2) -669(1) 22(1) C(7) 9356(4) 6142(2) -505(1) 28(1) C(8) 10320(4) 5652(2) -911(1) 31(1) C(9) 10446(4) 6006(2) -1495(1) 29(1) C(10) 9611(4) 6857(2) -1668(1) 28(1) C(11) 8661(4) 7375(2) -1266(1) 25(1) C(12) 7846(4) 8306(2) -1497(1) 30(1) C(13) 7303(6) 8427(3) -2121(2) 49(1) C(14) 5064(4) 6601(2) -746(1) 26(1) C(15) 4224(4) 6895(2) -1229(1) 26(1) C(16) 3477(4) 7859(2) -1339(1) 30(1) C(17) 3355(4) 8436(2) -829(1) 25(1) C(18) 2421(4) 9317(2) -852(2) 32(1) C(19) 2279(4) 9818(2) -362(2) 35(1) C(20) 3073(5) 9472(3) 149(2) 42(1) C(21) 4024(5) 8633(2) 171(2) 39(1) C(22) 4172(4) 8106(2) -308(1) 24(1) C(23) 819(9) 10540(4) -1399(2) 104(2) C(24) 3520(4) 6150(2) 549(1) 27(1) C(25) 3485(4) 5706(2) 1134(1) 27(1) C(26) 4841(4) 5744(2) 1500(1) 25(1) C(27) 6363(4) 6243(2) 1295(1) 22(1) S-14

C(28) 3315(5) 4817(3) 2272(2) 40(1) C(29) 7905(4) 6369(2) 1597(1) 23(1) C(30) 9245(4) 6864(2) 1317(1) 25(1) C(31) 9186(4) 7266(2) 723(1) 25(1) C(32) 7393(5) 6458(2) 2623(1) 35(1) C(33) 10026(6) 6866(4) 2986(2) 65(1) C(34) 2602(4) 7530(2) 5134(1) 23(1) C(35) 543(4) 7813(2) 5198(1) 23(1) C(36) 233(4) 8457(2) 4633(1) 22(1) C(37) 1714(4) 8455(2) 4248(1) 22(1) C(38) 3094(4) 7909(2) 4502(1) 22(1) C(39) 3661(4) 7926(2) 5592(1) 22(1) C(40) 4413(4) 8801(2) 5458(1) 27(1) C(41) 5268(4) 9232(2) 5871(1) 30(1) C(42) 5383(4) 8816(2) 6441(1) 29(1) C(43) 4642(4) 7947(2) 6587(1) 28(1) C(44) 3801(4) 7493(2) 6175(1) 24(1) C(45) 3066(4) 6544(2) 6377(1) 28(1) C(46) 2579(5) 6335(3) 7025(2) 41(1) C(47) 161(4) 8337(2) 5727(1) 25(1) C(48) -670(4) 7975(2) 6212(1) 27(1) C(49) -1292(4) 7005(2) 6284(1) 27(1) C(50) -1370(4) 6535(2) 5734(1) 24(1) C(51) -2314(4) 5710(2) 5708(1) 29(1) C(52) -2472(4) 5333(2) 5178(2) 31(1) C(53) -1639(4) 5735(2) 4669(2) 32(1) C(54) -668(4) 6522(2) 4689(1) 28(1) C(55) -535(4) 6936(2) 5213(1) 24(1) C(56) -3848(5) 4434(3) 6215(2) 47(1) C(57) -1232(4) 8936(2) 4447(1) 29(1) C(58) -1228(4) 9424(2) 3878(1) 30(1) C(59) 214(4) 9433(2) 3498(1) 28(1) C(60) 1771(4) 8923(2) 3671(1) 24(1) C(61) -1303(6) 10431(3) 2775(2) 54(1) C(62) 3377(4) 8797(2) 3344(1) 26(1) C(63) 4710(4) 8251(2) 3586(1) 29(1) C(64) 4604(4) 7799(2) 4170(1) 27(1) C(65) 4891(9) 9014(5) 2395(3) 44(2) C(66) 3176(10) 8191(6) 1800(3) 59(2) C(65') 2917(10) 8906(6) 2308(3) 31(2) C(66') 5493(12) 8663(7) 1773(4) 45(3) S-15

Table 3. Bond lengths [A] and angles [deg] for mx997. O(1)-C(12) 1.208(4) O(2)-C(16) 1.223(4) O(3)-C(18) 1.350(4) O(3)-C(23) 1.437(5) O(4)-C(26) 1.363(3) O(4)-C(28) 1.436(4) O(5)-C(29) 1.381(3) O(5)-C(32) 1.418(4) O(6)-C(32) 1.385(4) O(6)-C(33) 1.429(5) O(7)-C(45) 1.207(4) O(8)-C(49) 1.223(4) O(9)-C(51) 1.361(4) O(9)-C(56) 1.431(4) O(10)-C(59) 1.362(4) O(10)-C(61) 1.429(4) O(11)-C(62) 1.379(4) O(11)-C(65') 1.387(7) O(11)-C(65) 1.401(6) O(12)-C(66) 1.225(7) O(12)-C(66') 1.295(8) O(12)-C(65) 1.436(7) O(12)-C(65') 1.558(8) C(1)-C(5) 1.516(4) C(1)-C(6) 1.528(4) C(1)-C(2) 1.634(4) C(1)-H(1A) 1.0000 C(2)-C(14) 1.489(4) C(2)-C(22) 1.523(4) C(2)-C(3) 1.528(4) C(3)-C(24) 1.362(4) C(3)-C(4) 1.410(4) C(4)-C(5) 1.408(4) C(4)-C(27) 1.411(4) C(5)-C(31) 1.363(4) C(6)-C(7) 1.392(4) C(6)-C(11) 1.412(4) C(7)-C(8) 1.384(4) C(7)-H(7A) 0.9500 C(8)-C(9) 1.375(4) C(8)-H(8A) 0.9500 C(9)-C(10) 1.381(5) S-16

C(9)-H(9A) 0.9500 C(10)-C(11) 1.396(4) C(10)-H(10A) 0.9500 C(11)-C(12) 1.502(4) C(12)-C(13) 1.490(5) C(13)-H(13A) 0.9800 C(13)-H(13B) 0.9800 C(13)-H(13C) 0.9800 C(14)-C(15) 1.325(4) C(14)-H(14A) 0.9500 C(15)-C(16) 1.472(4) C(15)-H(15A) 0.9500 C(16)-C(17) 1.484(4) C(17)-C(22) 1.401(4) C(17)-C(18) 1.422(4) C(18)-C(19) 1.380(5) C(19)-C(20) 1.378(5) C(19)-H(19A) 0.9500 C(20)-C(21) 1.375(5) C(20)-H(20A) 0.9500 C(21)-C(22) 1.381(4) C(21)-H(21A) 0.9500 C(23)-H(23A) 0.9800 C(23)-H(23B) 0.9800 C(23)-H(23C) 0.9800 C(24)-C(25) 1.416(4) C(24)-H(24A) 0.9500 C(25)-C(26) 1.373(4) C(25)-H(25A) 0.9500 C(26)-C(27) 1.435(4) C(27)-C(29) 1.427(4) C(28)-H(28A) 0.9800 C(28)-H(28B) 0.9800 C(28)-H(28C) 0.9800 C(29)-C(30) 1.373(4) C(30)-C(31) 1.418(4) C(30)-H(30A) 0.9500 C(31)-H(31A) 0.9500 C(32)-H(32A) 0.9900 C(32)-H(32B) 0.9900 C(33)-H(33A) 0.9800 C(33)-H(33B) 0.9800 C(33)-H(33C) 0.9800 C(34)-C(39) 1.519(4) S-17

C(34)-C(38) 1.523(4) C(34)-C(35) 1.629(4) C(34)-H(34A) 1.0000 C(35)-C(47) 1.491(4) C(35)-C(55) 1.527(4) C(35)-C(36) 1.528(4) C(36)-C(57) 1.359(4) C(36)-C(37) 1.410(4) C(37)-C(38) 1.406(4) C(37)-C(60) 1.412(4) C(38)-C(64) 1.374(4) C(39)-C(40) 1.397(4) C(39)-C(44) 1.415(4) C(40)-C(41) 1.380(4) C(40)-H(40A) 0.9500 C(41)-C(42) 1.377(4) C(41)-H(41A) 0.9500 C(42)-C(43) 1.391(4) C(42)-H(42A) 0.9500 C(43)-C(44) 1.388(4) C(43)-H(43A) 0.9500 C(44)-C(45) 1.510(4) C(45)-C(46) 1.509(4) C(46)-H(46A) 0.9800 C(46)-H(46B) 0.9800 C(46)-H(46C) 0.9800 C(47)-C(48) 1.322(4) C(47)-H(47A) 0.9500 C(48)-C(49) 1.474(4) C(48)-H(48A) 0.9500 C(49)-C(50) 1.481(4) C(50)-C(55) 1.405(4) C(50)-C(51) 1.416(4) C(51)-C(52) 1.380(5) C(52)-C(53) 1.384(5) C(52)-H(52A) 0.9500 C(53)-C(54) 1.380(4) C(53)-H(53A) 0.9500 C(54)-C(55) 1.392(4) C(54)-H(54A) 0.9500 C(56)-H(56A) 0.9800 C(56)-H(56B) 0.9800 C(56)-H(56C) 0.9800 C(57)-C(58) 1.410(4) S-18

C(57)-H(57A) 0.9500 C(58)-C(59) 1.379(5) C(58)-H(58A) 0.9500 C(59)-C(60) 1.430(4) C(60)-C(62) 1.432(4) C(61)-H(61A) 0.9800 C(61)-H(61B) 0.9800 C(61)-H(61C) 0.9800 C(62)-C(63) 1.368(5) C(63)-C(64) 1.418(4) C(63)-H(63A) 0.9500 C(64)-H(64A) 0.9500 C(65)-H(65A) 0.9900 C(65)-H(65B) 0.9900 C(66)-H(66A) 0.9800 C(66)-H(66B) 0.9800 C(66)-H(66C) 0.9800 C(65')-H(65C) 0.9900 C(65')-H(65D) 0.9900 C(66')-H(66D) 0.9800 C(66')-H(66E) 0.9800 C(66')-H(66F) 0.9800 C(18)-O(3)-C(23) 117.2(3) C(26)-O(4)-C(28) 117.1(3) C(29)-O(5)-C(32) 115.4(2) C(32)-O(6)-C(33) 112.9(3) C(51)-O(9)-C(56) 117.3(3) C(59)-O(10)-C(61) 117.3(3) C(62)-O(11)-C(65') 119.6(4) C(62)-O(11)-C(65) 120.1(4) C(65')-O(11)-C(65) 68.1(4) C(66)-O(12)-C(66') 100.2(7) C(66)-O(12)-C(65) 124.7(6) C(66')-O(12)-C(65) 71.1(5) C(66)-O(12)-C(65') 69.7(5) C(66')-O(12)-C(65') 108.3(6) C(65)-O(12)-C(65') 62.7(4) C(5)-C(1)-C(6) 113.7(2) C(5)-C(1)-C(2) 104.0(2) C(6)-C(1)-C(2) 112.5(2) C(5)-C(1)-H(1A) 108.8 C(6)-C(1)-H(1A) 108.8 C(2)-C(1)-H(1A) 108.8 S-19

C(14)-C(2)-C(22) 113.0(2) C(14)-C(2)-C(3) 109.8(2) C(22)-C(2)-C(3) 110.9(2) C(14)-C(2)-C(1) 111.3(2) C(22)-C(2)-C(1) 109.1(2) C(3)-C(2)-C(1) 102.2(2) C(24)-C(3)-C(4) 119.0(3) C(24)-C(3)-C(2) 130.2(3) C(4)-C(3)-C(2) 110.7(3) C(5)-C(4)-C(3) 112.0(3) C(5)-C(4)-C(27) 124.4(3) C(3)-C(4)-C(27) 123.6(3) C(31)-C(5)-C(4) 118.9(3) C(31)-C(5)-C(1) 131.0(3) C(4)-C(5)-C(1) 110.1(3) C(7)-C(6)-C(11) 118.2(3) C(7)-C(6)-C(1) 119.5(3) C(11)-C(6)-C(1) 122.0(3) C(8)-C(7)-C(6) 121.8(3) C(8)-C(7)-H(7A) 119.1 C(6)-C(7)-H(7A) 119.1 C(9)-C(8)-C(7) 120.1(3) C(9)-C(8)-H(8A) 119.9 C(7)-C(8)-H(8A) 119.9 C(8)-C(9)-C(10) 119.1(3) C(8)-C(9)-H(9A) 120.4 C(10)-C(9)-H(9A) 120.4 C(9)-C(10)-C(11) 121.9(3) C(9)-C(10)-H(10A) 119.0 C(11)-C(10)-H(10A) 119.0 C(10)-C(11)-C(6) 118.8(3) C(10)-C(11)-C(12) 117.8(3) C(6)-C(11)-C(12) 123.5(3) O(1)-C(12)-C(13) 119.4(3) O(1)-C(12)-C(11) 122.1(3) C(13)-C(12)-C(11) 118.5(3) C(12)-C(13)-H(13A) 109.5 C(12)-C(13)-H(13B) 109.5 H(13A)-C(13)-H(13B) 109.5 C(12)-C(13)-H(13C) 109.5 H(13A)-C(13)-H(13C) 109.5 H(13B)-C(13)-H(13C) 109.5 C(15)-C(14)-C(2) 123.5(3) C(15)-C(14)-H(14A) 118.3 S-20

C(2)-C(14)-H(14A) 118.3 C(14)-C(15)-C(16) 122.9(3) C(14)-C(15)-H(15A) 118.6 C(16)-C(15)-H(15A) 118.6 O(2)-C(16)-C(15) 118.8(3) O(2)-C(16)-C(17) 124.7(3) C(15)-C(16)-C(17) 116.5(3) C(22)-C(17)-C(18) 118.5(3) C(22)-C(17)-C(16) 119.5(3) C(18)-C(17)-C(16) 121.9(3) O(3)-C(18)-C(19) 122.6(3) O(3)-C(18)-C(17) 117.1(3) C(19)-C(18)-C(17) 120.3(3) C(20)-C(19)-C(18) 120.0(3) C(20)-C(19)-H(19A) 120.0 C(18)-C(19)-H(19A) 120.0 C(21)-C(20)-C(19) 120.2(3) C(21)-C(20)-H(20A) 119.9 C(19)-C(20)-H(20A) 119.9 C(20)-C(21)-C(22) 121.4(3) C(20)-C(21)-H(21A) 119.3 C(22)-C(21)-H(21A) 119.3 C(21)-C(22)-C(17) 119.4(3) C(21)-C(22)-C(2) 118.4(3) C(17)-C(22)-C(2) 122.1(3) O(3)-C(23)-H(23A) 109.5 O(3)-C(23)-H(23B) 109.5 H(23A)-C(23)-H(23B) 109.5 O(3)-C(23)-H(23C) 109.5 H(23A)-C(23)-H(23C) 109.5 H(23B)-C(23)-H(23C) 109.5 C(3)-C(24)-C(25) 119.3(3) C(3)-C(24)-H(24A) 120.3 C(25)-C(24)-H(24A) 120.3 C(26)-C(25)-C(24) 122.2(3) C(26)-C(25)-H(25A) 118.9 C(24)-C(25)-H(25A) 118.9 O(4)-C(26)-C(25) 123.0(3) O(4)-C(26)-C(27) 116.7(3) C(25)-C(26)-C(27) 120.2(3) C(4)-C(27)-C(29) 114.8(3) C(4)-C(27)-C(26) 115.7(3) C(29)-C(27)-C(26) 129.5(3) O(4)-C(28)-H(28A) 109.5 S-21

O(4)-C(28)-H(28B) 109.5 H(28A)-C(28)-H(28B) 109.5 O(4)-C(28)-H(28C) 109.5 H(28A)-C(28)-H(28C) 109.5 H(28B)-C(28)-H(28C) 109.5 C(30)-C(29)-O(5) 118.0(3) C(30)-C(29)-C(27) 120.7(3) O(5)-C(29)-C(27) 121.2(3) C(29)-C(30)-C(31) 122.6(3) C(29)-C(30)-H(30A) 118.7 C(31)-C(30)-H(30A) 118.7 C(5)-C(31)-C(30) 118.6(3) C(5)-C(31)-H(31A) 120.7 C(30)-C(31)-H(31A) 120.7 O(6)-C(32)-O(5) 112.9(3) O(6)-C(32)-H(32A) 109.0 O(5)-C(32)-H(32A) 109.0 O(6)-C(32)-H(32B) 109.0 O(5)-C(32)-H(32B) 109.0 H(32A)-C(32)-H(32B) 107.8 O(6)-C(33)-H(33A) 109.5 O(6)-C(33)-H(33B) 109.5 H(33A)-C(33)-H(33B) 109.5 O(6)-C(33)-H(33C) 109.5 H(33A)-C(33)-H(33C) 109.5 H(33B)-C(33)-H(33C) 109.5 C(39)-C(34)-C(38) 113.3(2) C(39)-C(34)-C(35) 112.9(2) C(38)-C(34)-C(35) 103.3(2) C(39)-C(34)-H(34A) 109.1 C(38)-C(34)-H(34A) 109.1 C(35)-C(34)-H(34A) 109.1 C(47)-C(35)-C(55) 111.9(2) C(47)-C(35)-C(36) 110.4(2) C(55)-C(35)-C(36) 110.2(2) C(47)-C(35)-C(34) 110.9(2) C(55)-C(35)-C(34) 110.4(2) C(36)-C(35)-C(34) 102.8(2) C(57)-C(36)-C(37) 119.1(3) C(57)-C(36)-C(35) 130.1(3) C(37)-C(36)-C(35) 110.6(3) C(38)-C(37)-C(36) 111.7(3) C(38)-C(37)-C(60) 124.6(3) C(36)-C(37)-C(60) 123.6(3) S-22

C(64)-C(38)-C(37) 118.7(3) C(64)-C(38)-C(34) 130.7(3) C(37)-C(38)-C(34) 110.7(3) C(40)-C(39)-C(44) 117.3(3) C(40)-C(39)-C(34) 119.4(3) C(44)-C(39)-C(34) 123.0(3) C(41)-C(40)-C(39) 122.1(3) C(41)-C(40)-H(40A) 119.0 C(39)-C(40)-H(40A) 119.0 C(42)-C(41)-C(40) 120.6(3) C(42)-C(41)-H(41A) 119.7 C(40)-C(41)-H(41A) 119.7 C(41)-C(42)-C(43) 118.6(3) C(41)-C(42)-H(42A) 120.7 C(43)-C(42)-H(42A) 120.7 C(44)-C(43)-C(42) 121.8(3) C(44)-C(43)-H(43A) 119.1 C(42)-C(43)-H(43A) 119.1 C(43)-C(44)-C(39) 119.7(3) C(43)-C(44)-C(45) 117.5(3) C(39)-C(44)-C(45) 122.8(3) O(7)-C(45)-C(46) 120.0(3) O(7)-C(45)-C(44) 122.0(3) C(46)-C(45)-C(44) 118.0(3) C(45)-C(46)-H(46A) 109.5 C(45)-C(46)-H(46B) 109.5 H(46A)-C(46)-H(46B) 109.5 C(45)-C(46)-H(46C) 109.5 H(46A)-C(46)-H(46C) 109.5 H(46B)-C(46)-H(46C) 109.5 C(48)-C(47)-C(35) 123.6(3) C(48)-C(47)-H(47A) 118.2 C(35)-C(47)-H(47A) 118.2 C(47)-C(48)-C(49) 123.0(3) C(47)-C(48)-H(48A) 118.5 C(49)-C(48)-H(48A) 118.5 O(8)-C(49)-C(48) 119.3(3) O(8)-C(49)-C(50) 124.8(3) C(48)-C(49)-C(50) 115.9(3) C(55)-C(50)-C(51) 118.5(3) C(55)-C(50)-C(49) 119.3(3) C(51)-C(50)-C(49) 122.2(3) O(9)-C(51)-C(52) 122.5(3) O(9)-C(51)-C(50) 116.8(3) S-23

C(52)-C(51)-C(50) 120.6(3) C(51)-C(52)-C(53) 120.1(3) C(51)-C(52)-H(52A) 119.9 C(53)-C(52)-H(52A) 119.9 C(54)-C(53)-C(52) 120.0(3) C(54)-C(53)-H(53A) 120.0 C(52)-C(53)-H(53A) 120.0 C(53)-C(54)-C(55) 121.0(3) C(53)-C(54)-H(54A) 119.5 C(55)-C(54)-H(54A) 119.5 C(54)-C(55)-C(50) 119.6(3) C(54)-C(55)-C(35) 117.9(3) C(50)-C(55)-C(35) 122.5(3) O(9)-C(56)-H(56A) 109.5 O(9)-C(56)-H(56B) 109.5 H(56A)-C(56)-H(56B) 109.5 O(9)-C(56)-H(56C) 109.5 H(56A)-C(56)-H(56C) 109.5 H(56B)-C(56)-H(56C) 109.5 C(36)-C(57)-C(58) 119.3(3) C(36)-C(57)-H(57A) 120.4 C(58)-C(57)-H(57A) 120.4 C(59)-C(58)-C(57) 122.3(3) C(59)-C(58)-H(58A) 118.8 C(57)-C(58)-H(58A) 118.8 O(10)-C(59)-C(58) 122.9(3) O(10)-C(59)-C(60) 116.9(3) C(58)-C(59)-C(60) 120.2(3) C(37)-C(60)-C(59) 115.5(3) C(37)-C(60)-C(62) 114.7(3) C(59)-C(60)-C(62) 129.8(3) O(10)-C(61)-H(61A) 109.5 O(10)-C(61)-H(61B) 109.5 H(61A)-C(61)-H(61B) 109.5 O(10)-C(61)-H(61C) 109.5 H(61A)-C(61)-H(61C) 109.5 H(61B)-C(61)-H(61C) 109.5 C(63)-C(62)-O(11) 121.3(3) C(63)-C(62)-C(60) 120.9(3) O(11)-C(62)-C(60) 117.7(3) C(62)-C(63)-C(64) 122.7(3) C(62)-C(63)-H(63A) 118.7 C(64)-C(63)-H(63A) 118.7 C(38)-C(64)-C(63) 118.5(3) S-24

C(38)-C(64)-H(64A) 120.7 C(63)-C(64)-H(64A) 120.7 O(11)-C(65)-O(12) 109.3(4) O(11)-C(65)-H(65A) 109.8 O(12)-C(65)-H(65A) 109.8 O(11)-C(65)-H(65B) 109.8 O(12)-C(65)-H(65B) 109.8 H(65A)-C(65)-H(65B) 108.3 O(12)-C(66)-H(66A) 109.5 O(12)-C(66)-H(66B) 109.5 O(12)-C(66)-H(66C) 109.5 O(11)-C(65')-O(12) 103.5(5) O(11)-C(65')-H(65C) 111.1 O(12)-C(65')-H(65C) 111.1 O(11)-C(65')-H(65D) 111.1 O(12)-C(65')-H(65D) 111.1 H(65C)-C(65')-H(65D) 109.0 O(12)-C(66')-H(66D) 109.5 O(12)-C(66')-H(66E) 109.5 H(66D)-C(66')-H(66E) 109.5 O(12)-C(66')-H(66F) 109.5 H(66D)-C(66')-H(66F) 109.5 H(66E)-C(66')-H(66F) 109.5 Symmetry transformations used to generate equivalent atoms: S-25

Table 4. Anisotropic displacement parameters (A^2 x 10^3) for mx997. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 +... + 2 h k a* b* U12 ] U11 U22 U33 U23 U13 U12 O(1) 97(2) 31(1) 29(1) 3(1) 6(1) 21(1) O(2) 76(2) 51(2) 29(1) -7(1) -21(1) 25(2) O(3) 85(2) 55(2) 44(2) -11(1) -29(2) 44(2) O(4) 40(1) 36(1) 22(1) 4(1) 1(1) -11(1) O(5) 41(1) 27(1) 17(1) -2(1) -4(1) 2(1) O(6) 69(2) 42(2) 41(2) -16(1) -4(1) -5(1) O(7) 65(2) 27(1) 35(1) 0(1) -11(1) -11(1) O(8) 58(2) 46(2) 28(1) 1(1) 7(1) -17(1) O(9) 45(2) 34(1) 41(1) 2(1) 6(1) -19(1) O(10) 53(2) 42(1) 25(1) 4(1) -9(1) 12(1) O(11) 59(2) 30(1) 20(1) 0(1) 7(1) 0(1) O(12) 117(3) 42(2) 48(2) -17(1) 33(2) -9(2) C(1) 24(2) 21(2) 19(1) -1(1) -3(1) 0(1) C(2) 24(2) 26(2) 19(2) 1(1) -4(1) 6(1) C(3) 26(2) 21(2) 21(2) -3(1) -2(1) 5(1) C(4) 27(2) 19(2) 20(2) -4(1) 0(1) 4(1) C(5) 29(2) 20(2) 19(2) -5(1) 3(1) 0(1) C(6) 25(2) 22(2) 18(1) -2(1) -2(1) -4(1) C(7) 32(2) 27(2) 25(2) 1(1) 1(1) 5(1) C(8) 31(2) 27(2) 35(2) -6(1) -2(1) 3(1) C(9) 27(2) 34(2) 27(2) -8(1) 6(1) 1(1) C(10) 28(2) 34(2) 20(2) -2(1) 2(1) -4(1) C(11) 31(2) 24(2) 22(2) -1(1) 0(1) -3(1) C(12) 36(2) 26(2) 24(2) 6(1) 3(1) -3(1) C(13) 72(3) 39(2) 34(2) 5(2) -12(2) 5(2) C(14) 26(2) 25(2) 25(2) -3(1) 2(1) 2(1) C(15) 25(2) 27(2) 28(2) -8(1) -2(1) -1(1) C(16) 30(2) 37(2) 24(2) -2(1) -9(1) 4(1) C(17) 23(2) 26(2) 24(2) 0(1) -3(1) 3(1) C(18) 32(2) 30(2) 33(2) 3(1) -5(1) 8(1) C(19) 34(2) 30(2) 40(2) -6(2) 0(2) 11(2) C(20) 54(2) 39(2) 33(2) -13(2) -4(2) 17(2) C(21) 52(2) 37(2) 26(2) -6(2) -9(2) 14(2) C(22) 25(2) 24(2) 23(2) -1(1) -1(1) 1(1) C(23) 168(6) 82(4) 59(3) -15(3) -45(4) 94(4) C(24) 27(2) 27(2) 26(2) -2(1) -3(1) 0(1) C(25) 25(2) 28(2) 30(2) -4(1) 5(1) -4(1) C(26) 34(2) 21(2) 20(2) -2(1) 3(1) 0(1) C(27) 26(2) 20(2) 20(2) -3(1) 2(1) 2(1) S-26

C(28) 46(2) 42(2) 30(2) 3(2) 8(2) -14(2) C(29) 32(2) 22(2) 17(1) -5(1) -2(1) 4(1) C(30) 24(2) 29(2) 24(2) -5(1) -4(1) 3(1) C(31) 27(2) 24(2) 24(2) -3(1) -1(1) -3(1) C(32) 46(2) 38(2) 21(2) -7(1) 1(2) -2(2) C(33) 73(3) 82(3) 45(2) -18(2) -15(2) -27(3) C(34) 25(2) 22(2) 21(2) -2(1) 1(1) -2(1) C(35) 24(2) 23(2) 21(2) -4(1) 1(1) -6(1) C(36) 24(2) 20(2) 25(2) -6(1) 0(1) -4(1) C(37) 24(2) 18(1) 24(2) -6(1) -2(1) -2(1) C(38) 23(2) 22(2) 23(2) -6(1) -2(1) -4(1) C(39) 22(2) 22(2) 23(2) -4(1) 0(1) -2(1) C(40) 29(2) 28(2) 23(2) 1(1) -3(1) -1(1) C(41) 30(2) 27(2) 34(2) -3(1) -2(1) -7(1) C(42) 28(2) 33(2) 29(2) -8(1) -6(1) -3(1) C(43) 33(2) 31(2) 21(2) -2(1) -5(1) 2(1) C(44) 25(2) 23(2) 24(2) -2(1) 2(1) 2(1) C(45) 28(2) 25(2) 29(2) 4(1) -7(1) 0(1) C(46) 55(2) 33(2) 33(2) 7(2) 1(2) -6(2) C(47) 23(2) 23(2) 31(2) -6(1) 0(1) -4(1) C(48) 26(2) 30(2) 26(2) -11(1) 3(1) -1(1) C(49) 22(2) 32(2) 26(2) -2(1) 2(1) -3(1) C(50) 21(2) 23(2) 27(2) -2(1) -1(1) -1(1) C(51) 28(2) 28(2) 32(2) -1(1) 1(1) -5(1) C(52) 29(2) 22(2) 45(2) -5(1) -3(2) -7(1) C(53) 35(2) 30(2) 33(2) -12(1) -5(2) -1(2) C(54) 29(2) 28(2) 29(2) -4(1) -1(1) -5(1) C(55) 23(2) 24(2) 25(2) -3(1) -2(1) -1(1) C(56) 49(2) 33(2) 59(3) 1(2) 6(2) -18(2) C(57) 25(2) 26(2) 36(2) -7(1) 1(1) -1(1) C(58) 27(2) 26(2) 37(2) -7(1) -8(1) 2(1) C(59) 37(2) 24(2) 25(2) -6(1) -7(1) 0(1) C(60) 32(2) 20(2) 20(2) -6(1) -2(1) -2(1) C(61) 61(3) 58(3) 43(2) 2(2) -24(2) 16(2) C(62) 33(2) 26(2) 21(2) -6(1) 4(1) -6(1) C(63) 24(2) 33(2) 29(2) -10(1) 8(1) -3(1) C(64) 24(2) 31(2) 26(2) -7(1) -1(1) 2(1) C(65) 51(4) 52(4) 27(3) 3(3) 5(3) -13(3) C(66) 62(5) 72(5) 46(4) -23(4) -18(4) 18(4) C(65') 33(5) 37(5) 24(4) -6(3) -4(3) -1(4) C(66') 44(6) 47(6) 42(5) -8(4) 23(4) -4(4) S-27

Table 5. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for mx997. x y z U(eq) H(1A) 7410 8165-289 26 H(7A) 9272 5885-104 34 H(8A) 10895 5070-785 37 H(9A) 11097 5670-1775 35 H(10A) 9687 7097-2072 33 H(13A) 6238 8823-2147 73 H(13B) 7092 7809-2252 73 H(13C) 8223 8729-2373 73 H(14A) 5545 5975-710 31 H(15A) 4098 6465-1516 31 H(19A) 1635 10401-376 42 H(20A) 2964 9813 488 50 H(21A) 4592 8412 522 46 H(23A) 457 10715-1804 156 H(23B) 1607 11009-1288 156 H(23C) -203 10518-1128 156 H(24A) 2561 6114 306 32 H(25A) 2490 5371 1278 33 H(28A) 3434 4575 2687 60 H(28B) 3204 4288 2033 60 H(28C) 2280 5236 2235 60 H(30A) 10251 6940 1531 30 H(31A) 10135 7603 541 30 H(32A) 6236 6719 2507 42 H(32B) 7228 6018 2984 42 H(33A) 10534 7377 3171 98 H(33B) 10813 6673 2667 98 H(33C) 9845 6328 3282 98 H(34A) 2757 6827 5172 27 H(40A) 4333 9108 5069 32 H(41A) 5782 9822 5762 36 H(42A) 5956 9117 6728 35 H(43A) 4713 7656 6979 34 H(46A) 1676 5867 7073 61 H(46B) 2142 6916 7186 61 H(46C) 3602 6086 7237 61 H(47A) 537 8965 5716 30 H(48A) -877 8357 6529 32 H(52A) -3153 4797 5162 38 H(53A) -1735 5469 4306 39 S-28

H(54A) -81 6786 4339 34 H(56A) -4214 4196 6619 71 H(56B) -3020 3979 6051 71 H(56C) -4862 4521 5969 71 H(57A) -2247 8941 4699 34 H(58A) -2255 9759 3751 36 H(61A) -1116 10748 2377 82 H(61B) -1587 10903 3053 82 H(61C) -2263 10001 2777 82 H(63A) 5749 8171 3354 34 H(64A) 5555 7429 4327 32 H(65A) 5972 8866 2608 52 H(65B) 5109 9541 2087 52 H(66A) 3303 7635 1579 89 H(66B) 3163 8763 1524 89 H(66C) 2087 8166 2039 89 H(65C) 2696 9405 1983 37 H(65D) 1830 8575 2418 37 H(66D) 6073 8235 1508 67 H(66E) 6359 8928 2005 67 H(66F) 4879 9175 1538 67 S-29

Table 6. Torsion angles [deg] for mx997. C(5)-C(1)-C(2)-C(14) -126.2(3) C(6)-C(1)-C(2)-C(14) -2.7(3) C(5)-C(1)-C(2)-C(22) 108.4(3) C(6)-C(1)-C(2)-C(22) -128.1(3) C(5)-C(1)-C(2)-C(3) -9.1(3) C(6)-C(1)-C(2)-C(3) 114.4(3) C(14)-C(2)-C(3)-C(24) -56.1(4) C(22)-C(2)-C(3)-C(24) 69.5(4) C(1)-C(2)-C(3)-C(24) -174.3(3) C(14)-C(2)-C(3)-C(4) 126.3(3) C(22)-C(2)-C(3)-C(4) -108.1(3) C(1)-C(2)-C(3)-C(4) 8.1(3) C(24)-C(3)-C(4)-C(5) 178.2(3) C(2)-C(3)-C(4)-C(5) -3.9(3) C(24)-C(3)-C(4)-C(27) -1.5(4) C(2)-C(3)-C(4)-C(27) 176.4(3) C(3)-C(4)-C(5)-C(31) 178.8(3) C(27)-C(4)-C(5)-C(31) -1.5(5) C(3)-C(4)-C(5)-C(1) -2.8(3) C(27)-C(4)-C(5)-C(1) 177.0(3) C(6)-C(1)-C(5)-C(31) 63.1(4) C(2)-C(1)-C(5)-C(31) -174.2(3) C(6)-C(1)-C(5)-C(4) -115.1(3) C(2)-C(1)-C(5)-C(4) 7.6(3) C(5)-C(1)-C(6)-C(7) 23.8(4) C(2)-C(1)-C(6)-C(7) -94.2(3) C(5)-C(1)-C(6)-C(11) -161.8(3) C(2)-C(1)-C(6)-C(11) 80.2(3) C(11)-C(6)-C(7)-C(8) -0.5(5) C(1)-C(6)-C(7)-C(8) 174.1(3) C(6)-C(7)-C(8)-C(9) -0.7(5) C(7)-C(8)-C(9)-C(10) 0.5(5) C(8)-C(9)-C(10)-C(11) 0.8(5) C(9)-C(10)-C(11)-C(6) -2.0(5) C(9)-C(10)-C(11)-C(12) 178.3(3) C(7)-C(6)-C(11)-C(10) 1.8(4) C(1)-C(6)-C(11)-C(10) -172.7(3) C(7)-C(6)-C(11)-C(12) -178.5(3) C(1)-C(6)-C(11)-C(12) 7.0(5) C(10)-C(11)-C(12)-O(1) -151.3(3) C(6)-C(11)-C(12)-O(1) 29.0(5) C(10)-C(11)-C(12)-C(13) 30.1(5) S-30

C(6)-C(11)-C(12)-C(13) -149.6(3) C(22)-C(2)-C(14)-C(15) 11.5(4) C(3)-C(2)-C(14)-C(15) 135.9(3) C(1)-C(2)-C(14)-C(15) -111.7(3) C(2)-C(14)-C(15)-C(16) 2.0(5) C(14)-C(15)-C(16)-O(2) 165.8(3) C(14)-C(15)-C(16)-C(17) -13.2(5) O(2)-C(16)-C(17)-C(22) -169.3(3) C(15)-C(16)-C(17)-C(22) 9.7(4) O(2)-C(16)-C(17)-C(18) 11.1(5) C(15)-C(16)-C(17)-C(18) -170.0(3) C(23)-O(3)-C(18)-C(19) 2.9(6) C(23)-O(3)-C(18)-C(17) -177.2(4) C(22)-C(17)-C(18)-O(3) 178.0(3) C(16)-C(17)-C(18)-O(3) -2.4(5) C(22)-C(17)-C(18)-C(19) -2.1(5) C(16)-C(17)-C(18)-C(19) 177.5(3) O(3)-C(18)-C(19)-C(20) -178.9(4) C(17)-C(18)-C(19)-C(20) 1.2(5) C(18)-C(19)-C(20)-C(21) 0.7(6) C(19)-C(20)-C(21)-C(22) -1.8(6) C(20)-C(21)-C(22)-C(17) 0.8(5) C(20)-C(21)-C(22)-C(2) 178.1(3) C(18)-C(17)-C(22)-C(21) 1.1(5) C(16)-C(17)-C(22)-C(21) -178.6(3) C(18)-C(17)-C(22)-C(2) -176.1(3) C(16)-C(17)-C(22)-C(2) 4.2(4) C(14)-C(2)-C(22)-C(21) 168.3(3) C(3)-C(2)-C(22)-C(21) 44.5(4) C(1)-C(2)-C(22)-C(21) -67.3(3) C(14)-C(2)-C(22)-C(17) -14.5(4) C(3)-C(2)-C(22)-C(17) -138.3(3) C(1)-C(2)-C(22)-C(17) 109.9(3) C(4)-C(3)-C(24)-C(25) 0.5(4) C(2)-C(3)-C(24)-C(25) -177.0(3) C(3)-C(24)-C(25)-C(26) 0.3(5) C(28)-O(4)-C(26)-C(25) 1.8(4) C(28)-O(4)-C(26)-C(27) -178.9(3) C(24)-C(25)-C(26)-O(4) 179.1(3) C(24)-C(25)-C(26)-C(27) -0.1(5) C(5)-C(4)-C(27)-C(29) 1.2(4) C(3)-C(4)-C(27)-C(29) -179.1(3) C(5)-C(4)-C(27)-C(26) -178.1(3) C(3)-C(4)-C(27)-C(26) 1.6(4) S-31

O(4)-C(26)-C(27)-C(4) 179.9(3) C(25)-C(26)-C(27)-C(4) -0.8(4) O(4)-C(26)-C(27)-C(29) 0.8(5) C(25)-C(26)-C(27)-C(29) -179.9(3) C(32)-O(5)-C(29)-C(30) 99.4(3) C(32)-O(5)-C(29)-C(27) -84.5(3) C(4)-C(27)-C(29)-C(30) -0.2(4) C(26)-C(27)-C(29)-C(30) 178.9(3) C(4)-C(27)-C(29)-O(5) -176.2(3) C(26)-C(27)-C(29)-O(5) 2.9(5) O(5)-C(29)-C(30)-C(31) 175.7(3) C(27)-C(29)-C(30)-C(31) -0.4(5) C(4)-C(5)-C(31)-C(30) 0.8(4) C(1)-C(5)-C(31)-C(30) -177.3(3) C(29)-C(30)-C(31)-C(5) 0.1(5) C(33)-O(6)-C(32)-O(5) -65.4(4) C(29)-O(5)-C(32)-O(6) -80.0(4) C(39)-C(34)-C(35)-C(47) -4.5(3) C(38)-C(34)-C(35)-C(47) -127.3(3) C(39)-C(34)-C(35)-C(55) -129.1(3) C(38)-C(34)-C(35)-C(55) 108.2(3) C(39)-C(34)-C(35)-C(36) 113.4(3) C(38)-C(34)-C(35)-C(36) -9.3(3) C(47)-C(35)-C(36)-C(57) -59.4(4) C(55)-C(35)-C(36)-C(57) 64.7(4) C(34)-C(35)-C(36)-C(57) -177.7(3) C(47)-C(35)-C(36)-C(37) 126.4(3) C(55)-C(35)-C(36)-C(37) -109.5(3) C(34)-C(35)-C(36)-C(37) 8.1(3) C(57)-C(36)-C(37)-C(38) -178.5(3) C(35)-C(36)-C(37)-C(38) -3.5(3) C(57)-C(36)-C(37)-C(60) -0.3(4) C(35)-C(36)-C(37)-C(60) 174.7(3) C(36)-C(37)-C(38)-C(64) 176.8(3) C(60)-C(37)-C(38)-C(64) -1.4(4) C(36)-C(37)-C(38)-C(34) -3.2(3) C(60)-C(37)-C(38)-C(34) 178.5(3) C(39)-C(34)-C(38)-C(64) 65.5(4) C(35)-C(34)-C(38)-C(64) -172.1(3) C(39)-C(34)-C(38)-C(37) -114.5(3) C(35)-C(34)-C(38)-C(37) 8.0(3) C(38)-C(34)-C(39)-C(40) 24.8(4) C(35)-C(34)-C(39)-C(40) -92.2(3) C(38)-C(34)-C(39)-C(44) -161.2(3) S-32

C(35)-C(34)-C(39)-C(44) 81.8(4) C(44)-C(39)-C(40)-C(41) 0.3(5) C(34)-C(39)-C(40)-C(41) 174.6(3) C(39)-C(40)-C(41)-C(42) -1.2(5) C(40)-C(41)-C(42)-C(43) 0.9(5) C(41)-C(42)-C(43)-C(44) 0.1(5) C(42)-C(43)-C(44)-C(39) -1.0(5) C(42)-C(43)-C(44)-C(45) 179.1(3) C(40)-C(39)-C(44)-C(43) 0.8(4) C(34)-C(39)-C(44)-C(43) -173.3(3) C(40)-C(39)-C(44)-C(45) -179.3(3) C(34)-C(39)-C(44)-C(45) 6.6(5) C(43)-C(44)-C(45)-O(7) -153.7(3) C(39)-C(44)-C(45)-O(7) 26.4(5) C(43)-C(44)-C(45)-C(46) 26.0(4) C(39)-C(44)-C(45)-C(46) -153.9(3) C(55)-C(35)-C(47)-C(48) 15.3(4) C(36)-C(35)-C(47)-C(48) 138.4(3) C(34)-C(35)-C(47)-C(48) -108.3(3) C(35)-C(47)-C(48)-C(49) 0.8(5) C(47)-C(48)-C(49)-O(8) 163.8(3) C(47)-C(48)-C(49)-C(50) -16.0(5) O(8)-C(49)-C(50)-C(55) -166.6(3) C(48)-C(49)-C(50)-C(55) 13.2(4) O(8)-C(49)-C(50)-C(51) 15.8(5) C(48)-C(49)-C(50)-C(51) -164.4(3) C(56)-O(9)-C(51)-C(52) 6.1(5) C(56)-O(9)-C(51)-C(50) -173.9(3) C(55)-C(50)-C(51)-O(9) 177.1(3) C(49)-C(50)-C(51)-O(9) -5.2(5) C(55)-C(50)-C(51)-C(52) -2.8(5) C(49)-C(50)-C(51)-C(52) 174.8(3) O(9)-C(51)-C(52)-C(53) -177.0(3) C(50)-C(51)-C(52)-C(53) 3.0(5) C(51)-C(52)-C(53)-C(54) -0.9(5) C(52)-C(53)-C(54)-C(55) -1.3(5) C(53)-C(54)-C(55)-C(50) 1.4(5) C(53)-C(54)-C(55)-C(35) -179.1(3) C(51)-C(50)-C(55)-C(54) 0.6(4) C(49)-C(50)-C(55)-C(54) -177.1(3) C(51)-C(50)-C(55)-C(35) -178.8(3) C(49)-C(50)-C(55)-C(35) 3.5(4) C(47)-C(35)-C(55)-C(54) 163.2(3) C(36)-C(35)-C(55)-C(54) 40.0(4) S-33

C(34)-C(35)-C(55)-C(54) -72.8(3) C(47)-C(35)-C(55)-C(50) -17.3(4) C(36)-C(35)-C(55)-C(50) -140.5(3) C(34)-C(35)-C(55)-C(50) 106.6(3) C(37)-C(36)-C(57)-C(58) -0.6(4) C(35)-C(36)-C(57)-C(58) -174.4(3) C(36)-C(57)-C(58)-C(59) 0.2(5) C(61)-O(10)-C(59)-C(58) 1.7(5) C(61)-O(10)-C(59)-C(60) -178.9(3) C(57)-C(58)-C(59)-O(10) -179.6(3) C(57)-C(58)-C(59)-C(60) 1.0(5) C(38)-C(37)-C(60)-C(59) 179.4(3) C(36)-C(37)-C(60)-C(59) 1.4(4) C(38)-C(37)-C(60)-C(62) 0.6(4) C(36)-C(37)-C(60)-C(62) -177.4(3) O(10)-C(59)-C(60)-C(37) 178.8(3) C(58)-C(59)-C(60)-C(37) -1.8(4) O(10)-C(59)-C(60)-C(62) -2.6(5) C(58)-C(59)-C(60)-C(62) 176.8(3) C(65')-O(11)-C(62)-C(63) 99.3(5) C(65)-O(11)-C(62)-C(63) 18.8(5) C(65')-O(11)-C(62)-C(60) -83.7(5) C(65)-O(11)-C(62)-C(60) -164.1(4) C(37)-C(60)-C(62)-C(63) 0.8(4) C(59)-C(60)-C(62)-C(63) -177.8(3) C(37)-C(60)-C(62)-O(11) -176.3(3) C(59)-C(60)-C(62)-O(11) 5.1(5) O(11)-C(62)-C(63)-C(64) 175.5(3) C(60)-C(62)-C(63)-C(64) -1.4(5) C(37)-C(38)-C(64)-C(63) 0.8(4) C(34)-C(38)-C(64)-C(63) -179.2(3) C(62)-C(63)-C(64)-C(38) 0.6(5) C(62)-O(11)-C(65)-O(12) 79.2(5) C(65')-O(11)-C(65)-O(12) -33.3(5) C(66)-O(12)-C(65)-O(11) 64.5(7) C(66')-O(12)-C(65)-O(11) 154.0(7) C(65')-O(12)-C(65)-O(11) 30.7(5) C(62)-O(11)-C(65')-O(12) -83.7(5) C(65)-O(11)-C(65')-O(12) 29.4(4) C(66)-O(12)-C(65')-O(11) 179.2(7) C(66')-O(12)-C(65')-O(11) -86.4(7) C(65)-O(12)-C(65')-O(11) -30.0(4) Symmetry transformations used to generate equivalent atoms: S-34

Table 7. Hydrogen bonds for mx997 [A and deg.]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) S-35

The X-ray structure of compound 4b S-36

Table 1. Crystal data and structure refinement for sx2948. Identification code sx2948 Empirical formula C33 H28 O6 Formula weight 520.55 Temperature 173(2) K Wavelength 1.54186 A Crystal system, space group Monoclinic, P2(1) Unit cell dimensions a = 8.1397(8) A alpha = 90 deg. b = 32.018(3) A beta = 97.590(7) deg. c = 9.9603(11) A gamma = 90 deg. Volume 2573.0(5) A^3 Z, Calculated density 4, 1.344 Mg/m^3 Absorption coefficient 0.748 mm^-1 F(000) 1096 Crystal size 0.80 x 0.50 x 0.30 mm Theta range for data collection 4.48 to 68.25 deg. Limiting indices -9<=h<=9, -36<=k<=38, -11<=l<=11 Reflections collected / unique 24362 / 9172 [R(int) = 0.0365] Completeness to theta = 68.25 99.9 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.8068 and 0.5861 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 9172 / 1 / 711 Goodness-of-fit on F^2 1.144 Final R indices [I>2sigma(I)] R1 = 0.0579, wr2 = 0.1397 R indices (all data) R1 = 0.0649, wr2 = 0.1469 Absolute structure parameter -0.2(2) Largest diff. peak and hole 0.786 and -0.370 e.a^-3 S-37

Table 2. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for sx2948. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) O(1) -1075(4) 152(1) 3701(3) 41(1) O(2) -2793(3) 1306(1) 6620(2) 37(1) O(3) -894(3) 1708(1) 8565(2) 32(1) O(4) 5360(3) 1969(1) 851(2) 30(1) O(5) 6585(3) 1190(1) 747(2) 30(1) O(6) 7726(6) 595(1) -117(5) 94(2) O(7) 12345(3) 4443(1) 2131(3) 39(1) O(8) 13987(3) 3329(1) -661(3) 40(1) O(9) 12086(3) 2932(1) -2629(3) 35(1) O(10) 5841(3) 2663(1) 5082(2) 30(1) O(11) 4635(3) 3436(1) 5238(2) 33(1) O(12) 3781(5) 4051(1) 6267(4) 72(1) C(1) 1671(4) 780(1) 4073(3) 25(1) C(2) 1108(4) 1255(1) 4327(3) 23(1) C(3) 2163(4) 1509(1) 3459(3) 22(1) C(4) 3278(4) 1244(1) 2892(3) 20(1) C(5) 3109(4) 828(1) 3281(3) 24(1) C(6) 1899(4) 519(1) 5341(3) 23(1) C(7) 592(4) 300(1) 5797(4) 25(1) C(8) 788(5) 119(1) 7083(4) 32(1) C(9) 2316(5) 130(1) 7888(4) 36(1) C(10) 3643(5) 320(1) 7414(4) 33(1) C(11) 3426(4) 521(1) 6166(4) 30(1) C(12) -1024(5) 214(1) 4908(4) 31(1) C(13) -2582(5) 205(2) 5551(5) 50(1) C(14) -712(4) 1279(1) 3739(3) 25(1) C(15) -1934(4) 1316(1) 4490(3) 27(1) C(16) -1649(4) 1354(1) 5959(3) 24(1) C(17) 85(4) 1464(1) 6569(3) 20(1) C(18) 430(4) 1626(1) 7900(3) 25(1) C(19) 2058(4) 1700(1) 8445(4) 31(1) C(20) 3327(4) 1625(1) 7690(4) 31(1) C(21) 3003(4) 1483(1) 6381(3) 24(1) C(22) 1392(4) 1404(1) 5800(3) 21(1) C(23) -584(6) 1911(2) 9856(4) 45(1) C(24) 2216(5) 1928(1) 3211(3) 27(1) C(25) 3297(5) 2085(1) 2354(4) 29(1) C(26) 4348(4) 1826(1) 1740(3) 23(1) C(27) 4403(4) 1389(1) 2026(3) 21(1) S-38

C(28) 5423(4) 1073(1) 1559(3) 24(1) C(29) 5306(4) 663(1) 1975(4) 31(1) C(30) 4129(5) 535(1) 2819(4) 30(1) C(31) 5141(5) 2385(1) 380(4) 37(1) C(32) 6719(6) 942(2) -403(5) 53(1) C(33) 9432(8) 691(2) 16(7) 88(2) C(34) 9476(4) 3858(1) 1834(4) 25(1) C(35) 10073(4) 3378(1) 1589(3) 24(1) C(36) 8994(4) 3126(1) 2442(3) 22(1) C(37) 7909(4) 3387(1) 3037(3) 21(1) C(38) 8053(4) 3805(1) 2666(3) 24(1) C(39) 9178(4) 4125(1) 575(3) 25(1) C(40) 7629(4) 4131(1) -197(4) 31(1) C(41) 7320(5) 4358(1) -1380(4) 37(1) C(42) 8568(5) 4581(1) -1851(4) 40(1) C(43) 10124(5) 4580(1) -1121(4) 35(1) C(44) 10461(4) 4364(1) 102(4) 28(1) C(45) 12117(5) 4423(1) 901(4) 34(1) C(46) 13611(5) 4470(2) 131(5) 52(1) C(47) 11847(4) 3357(1) 2190(4) 28(1) C(48) 13081(4) 3316(1) 1453(3) 26(1) C(49) 12816(4) 3275(1) -12(3) 24(1) C(50) 11116(4) 3174(1) -643(3) 23(1) C(51) 10754(4) 3015(1) -1975(3) 25(1) C(52) 9147(4) 2937(1) -2545(3) 27(1) C(53) 7855(4) 3018(1) -1798(4) 28(1) C(54) 8161(4) 3157(1) -465(4) 27(1) C(55) 9781(4) 3232(1) 108(3) 20(1) C(56) 11771(5) 2751(1) -3952(4) 40(1) C(57) 8974(4) 2706(1) 2688(4) 27(1) C(58) 7893(4) 2549(1) 3581(4) 26(1) C(59) 6853(4) 2803(1) 4193(3) 22(1) C(60) 6798(4) 3243(1) 3919(3) 20(1) C(61) 5771(4) 3561(1) 4404(3) 26(1) C(62) 5894(5) 3965(1) 4000(4) 33(1) C(63) 7047(5) 4094(1) 3136(4) 36(1) C(64) 6047(5) 2239(1) 5526(4) 34(1) C(65) 4538(7) 3677(1) 6378(5) 53(1) C(66) 1939(8) 3994(2) 6008(7) 80(2) S-39

Table 3. Bond lengths [A] and angles [deg] for sx2948. O(1)-C(12) 1.214(5) O(2)-C(16) 1.219(4) O(3)-C(18) 1.362(4) O(3)-C(23) 1.433(4) O(4)-C(26) 1.365(4) O(4)-C(31) 1.417(4) O(5)-C(28) 1.375(4) O(5)-C(32) 1.411(5) O(6)-C(32) 1.386(6) O(6)-C(33) 1.411(8) O(7)-C(45) 1.216(5) O(8)-C(49) 1.233(4) O(9)-C(51) 1.362(4) O(9)-C(56) 1.433(4) O(10)-C(59) 1.363(4) O(10)-C(64) 1.429(4) O(11)-C(61) 1.381(4) O(11)-C(65) 1.384(5) O(12)-C(65) 1.345(6) O(12)-C(66) 1.499(7) C(1)-C(5) 1.503(4) C(1)-C(6) 1.506(5) C(1)-C(2) 1.618(5) C(1)-H(1) 1.0000 C(2)-C(14) 1.521(5) C(2)-C(22) 1.530(5) C(2)-C(3) 1.530(5) C(3)-C(24) 1.368(5) C(3)-C(4) 1.413(4) C(4)-C(5) 1.398(5) C(4)-C(27) 1.416(4) C(5)-C(30) 1.373(5) C(6)-C(11) 1.397(5) C(6)-C(7) 1.398(5) C(7)-C(8) 1.396(5) C(7)-C(12) 1.511(5) C(8)-C(9) 1.388(6) C(8)-H(8) 0.9500 C(9)-C(10) 1.377(5) C(9)-H(9) 0.9500 C(10)-C(11) 1.389(5) C(10)-H(10) 0.9500 S-40