Alquenos altamente piramidalizados funcionalizados: generación, transformaciones y estudios relacionados 

Alquenos altamente piramidalizados funcionalizados:

generación, transformaciones y estudios relacionados

Mª Rosa Muñoz Blasco

Aquesta tesi doctoral està subjecta a la llicència Reconeixement- NoComercial 4.0. Espanya de Creative Commons.

Esta tesis doctoral está sujeta a la licencia Reconocimiento - NoComercial 4.0. España de Creative Commons.

This doctoral thesis is licensed under the Creative Commons Attribution-NonCommercial 4.0. Spain License.

Anexo 1.

1 4 5 6 7 8 1' 2' 6' 1'' _2'' 3'' 4'' 5'' 6'' 111 N N NH2 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

1 4 5 6 7 8 1' 2' 6' 1'' _2'' 3'' 4'' 5'' 6'' 111 N N NH2 13_C-DEPT 1_H-1_H-COSY

1 4 5 6 7 8 1' 2' 6' 1'' _2'' 3'' 4'' 5'' 6'' 111 N N NH2 1_H-1_{H-NOESY 0.5} 1_H-1_{H-NOESY 0.8}

1 4 5 6 7 8 1' 2' 6' 1'' _2'' 3'' 4'' 5'' 6'' 111 N N NH2 1_H-13_C-HSQC 1_H-13_{C-HMBC J=5 Hz}

1 4 5 6 7 8 1' 2' 6' 1'' _2'' 3'' 4'' 5'' 6'' 111 N N NH2 1_H-13_{C-HMBC J=8 Hz} IR (KBr)

I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' + sin-112 anti-112 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' + sin-112 anti-112 13_C-DEPT 1_H-1_H-COSY

I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' + sin-112 anti-112 1_H-13_C-HSQC 1_H-13_{C-HMBC J = 3 Hz}

I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' I I 1 2 3 4 5 6 7 8 2'' 3'' 4'' 2' _3' 4' + sin-112 anti-112 1_H-13_{C-HMBC J = 8 Hz} IR (KBr)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (50.3 MHz, CDCl} 3)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 13_C-DEPT 1_H-1_H-COSY

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_H-1_H-NOESY 1_H-13_C-HSQC

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 3 Hz}

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 IR (KBr)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (50.3 MHz, CDCl} 3)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_H-1_H-COSY 1_H-1_H-NOESY

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_H-13_C-HSQC 1_H-13_{C-HMBC J = 8 Hz}

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 2'' 3'' + sin-114 anti-114 1_H-13_{C-HMBC J= 3 Hz}

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,endo-105 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,endo-105 13_C-DEPT 1_H-1_H-COSY

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,endo-105 1_H-1_H-NOESY 1_H-13_C-HSQC

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,endo-105 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5Hz}

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,endo-105 IR (KBr)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,exo-105 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,exo-105 1_H-1_H-COSY 1_H-1_H-NOESY

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,exo-105 1_H-13_C-HSQC 1_H-13_{C-HMBC J = 8 Hz}

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' endo,exo-105 1_H-13_{C-HMBC J = 5 Hz} IR (KBr)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' exo,exo-105 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' exo,exo-105 1_H-1_H-COSY 1_H-1_H-NOESY

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' exo,exo-105 1_H-13_C-HSQC 1_H-13_{C-HMBC J = 8 Hz}

MeOOC COOMe 1 2 3 4 5 6 7 8 2' _3' 4' 2'' 3'' exo,exo-105 1_H-13_{C-HMBC J = 5 Hz} IR (KBr)

COOMe COOMe 106 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl )}

COOMe COOMe 106 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 13_C-DEPT 1_H-1_H-COSY

COOMe COOMe 106 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-1_H-NOESY 1_H-13_C-HSQC

COOMe COOMe 106 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

COOMe COOMe 106 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' IR (KBr)

COOH COOH 120 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_{H-RMN (500 MHz, DMSO-d} 6) 13_{C-RMN (100.6 MHz, DMSO-d} 6)

COOH COOH 120 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 13_C-DEPT 1_H-1_H-COSY

COOH COOH 120 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-13_C-HSQC IR (KBr)

O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 121 1_{H-RMN (300 MHz, DMSO-d} 6) 13_{C-RMN (75.4 MHz, DMSO-d} 6)

O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 121 13_C-DEPT 1_H-1_H-COSY

O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 121 1_H-13_C-HSQC IR (KBr)

COOH COOMe 122 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_{H-RMN (500 MHz, CD} 3OD) 13_{C-RMN (50.3 MHz, CDCl} 3 + gotas CD3OD)

COOH COOMe 122 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 13_C-DEPT 1_H-1_H-COSY

COOH COOMe 122 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-1_H-NOESY 1_H-13_C-HSQC

COOH COOMe 122 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

COOH COOMe 122 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' IR (KBr)

COOH O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' a b c d 125 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3 )

COOH O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' a b c d 125 13_C-DEPT 1_H-1_H-COSY

COOH O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' a b c d 125 1_H-1_H-NOESY 1_H-13_C-HSQC

COOH O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' a b c d 125 1_H-13_{C-HMBC J = 60 ms} 1_H-13_{C-HMBC J = 110 ms}

COOH O O 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' a b c d 125 IR (KBr)

COOMe I 123 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

COOMe I 123 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 13_C-DEPT 1_H-1_H-COSY

COOMe I 123 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-1_H-NOESY 1_H-13_C-HSQC

COOMe I 123 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

COOMe I 123 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' IR (KBr)

I O 6' 3 1 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' b d 126 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3 )

I O 6' 3 1 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' b d 126 13_C-DEPT 1_H-1_H-COSY

I O 6' 3 1 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' b d 126 1_H-1_H-NOESY 1_H-13_C-HSQC

I O 6' 3 1 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' b d 126 1_H-13_{C-HMBC J = 60 ms} 1_H-13_{C-HMBC J = 110 ms}

I O 6' 3 1 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' b d 126 IR (KBr)

COOH I 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 124 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

COOH I 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 124 1_H-1_H-COSY 1_H-1_{H- NOESY}

COOH I 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 124 1_H-13_C-HSQC 1_H-13_{C-HMBC J = 8 Hz}

COOH I 1 3 4 ₅ 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 124 1_H-13_{C-HMBC J= 5 Hz} IR (KBr)

I I 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 76 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

I I 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 76 13_C-DEPT 1_H-1_H-COSY

I I 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 76 1_H-1_H-NOESY 1_H-13_C-HSQC

I I 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 76 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

I I 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 76 IR (KBr)

3 H₃COOC COOH 127 1 4 ₅ 6 7 8 1_{H-RMN (300 MHz, CD} 3OD) 13_{C-RMN (75.4 MHz, CD} 3OD)

3 H₃COOC COOH 127 1 4 ₅ 6 7 8 13_C-DEPT IR (KBr)

I COOMe 4 ₅ 6 7 8 82 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

I COOMe 4 ₅ 6 7 8 82 13_C-DEPT 400 0,0 300 0 2000 1 500 1 000 450,0 20,0 25 30 35 40 45 50 55 60 64,0 cm-1 %T 3441,58 2997,81 2949,64 2899,86 2841,72 1745,83 1729,36 1482,19 1434,94 1334,26 1303,86 1270,73 1241,73 1215,78 1166,09 1131,76 1081,99 1016,19 996,04 983,03 963,94 946,62 862,84 837,84 817,34 794,66 781,10 754,52 645,66 618,13 569,07 463,25 IR (KBr)

I COOH 4 ₅ 6 7 8 128 1_{H-RMN (300 MHz, CD} 3OD) 13_{C-RMN (75.4 MHz, CD} 3OD)

I COOH 4 ₅ 6 7 8 128 13_C-DEPT IR (KBr)

I I 4 ₅ 6 7 8 77 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

I I 4 ₅ 6 7 8 77 IR (KBr)

I 141 OH 1_{H-RMN (300 MHz, CD} 3OD) 13_{C-RMN (75.4 MHz, CD} 3OD)

I 141 OH 13_C-DEPT 44 00,0 4000 30 00 2000 1500 10 00 450,0 4,8 6 8 10 12 14 16 18 20 22 24 26 28 30 31 ,6 cm-1 %T 3342,88 3267,37 2992,86 2979,95 2965,73 2935,77 2915,20 2887,04 2830,74 1508,19 1499,10 1474,02 1460,63 1437,80 1348,15 1316,48 1286,30 1267,78 1230,60 1216,09 1182,66 1133,75 1113,73 1086,32 1029,87 1015,98 978,13 959,21 932,21 894,35 827,54 809,09 737,26 700,52 632,48 587,01 IR (KBr)

4 ₅ 6 7 8 I O 78 1_{H- RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

4 ₅ 6 7 8 I O 78 13_{C-DEPT (75.4 MHz, CDCl} 3) IR (KBr)

4 ₅ 6 7 8 _O I 79 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

4 ₅ 6 7 8 _O I 79 13_C-DEPT 44 00,0 4000 3000 2000 15 00 10 00 450,0 7,4 10 12 14 16 18 20 22 24 26 28 30 32 34,1 cm-1 %T 3424,26 2975,80 2937,71 2914,60 2889,64 2851,65 1507,72 1473,95 1456,15 1347,78 1292,27 1282,21 1261,51 1236,15 1221,04 1178,05 1160,25 1141,90 1100,93 1075,95 1023,93 1004,17 981,08 969,78 946,88 923,52 902,41 889,98 829,94 793,49 712,19 672,79 615,44 541,82 491,62 IR (KBr)

142 I _OTs 1_{H-RMN (400 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

142 I _OTs 13_C-DEPT 4000,0 3000 2 00 0 1 50 0 1 00 0 4 50 ,0 3 ,0 5 1 0 1 5 2 0 2 5 3 0 3 5 38,0 cm-1 %T 3428,45 3053,57 2967,16 2923,18 2888,10 2854,17 1924,51 1733,95 1653,90 1597,81 1476,49 1461,51 1364,41 1354,27 1309,54 1296,09 1268,44 1241,36 1192,30 1177,90 1172,07 1135,13 1121,72 1096,39 1018,02 1007,77 961,01 889,65 845,93 836,61 825,26 814,56 792,10 705,63 677,77 665,99 658,08 617,60 553,19 516,02 482,83 IR (KBr)

I I 80 1 3 4 ₅ 6 7 8 _NH O 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, DMSO-d} 6)

I I 80 1 3 4 ₅ 6 7 8 _NH O 13_C-DEPT 4400,0 4 00 0 3000 2 00 0 1500 1 00 0 4 50 ,0 10,0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 66,0 cm-1 %T 3200 3074 2996 2946 2760 1768 1706 1475 1381 1341 1311 1273 1234 1211 1143 1097 1069 1055 997 961 835 775 731 707 639 617 521 IR (KBr)

I I 81 1 3 4 ₅ 6 7 8 _N O 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

I I 81 1 3 4 ₅ 6 7 8 _N O 13_C-DEPT 400 0,0 3 00 0 2 00 0 1 50 0 1 000 4 50 ,0 6,0 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5,0 cm-1 %T 3522 3448 2995 2946 2907 1764 1699 1457 1419 1372 1318 1266 1244 1168 1126 1114 1012 975 964 878 850 836 795 735 634 619 601 IR (KBr)

4 5 6 7 8 O S O O HOOC 104 1_{H-RMN (300 MHz, CD} 3OD) 13_{C-RMN (75.4 MHz, CD OD)}

1 2 3 4 5 6 7 8 O O S O O HOOC HOOC 104 IR (KBr)

83 1 2 3 4 5 6 7 8 O O S O O I I 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

83 1 2 3 4 5 6 7 8 O O S O O I I 13_{C-DEPT (75.4 MHz, CDCl} 3) IR (KBr)

H_α H_β O 146 8 7 17 4 5 16 2 1 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 3' 4' 5' 6' 14 13 ₁₂ 11 10 9 15 3 6 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

H_α H_β O 146 8 7 17 4 5 16 2 1 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 3' 4' 5' 6' 14 13 ₁₂ 11 10 9 15 3 6 13_C-DEPT 1_H-1_H-COSY

H_α H_β O 146 8 7 17 4 5 16 2 1 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 3' 4' 5' 6' 14 13 ₁₂ 11 10 9 15 3 6 1_H-1_H-NOESY 1_H-13_C-HSQC

H_α H_β O 146 8 7 17 4 5 16 2 1 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 3' 4' 5' 6' 14 13 ₁₂ 11 10 9 15 3 6 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

H_α H_β O 146 8 7 17 4 5 16 2 1 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 3' 4' 5' 6' 14 13 ₁₂ 11 10 9 15 3 6 IR (KBr)

147 1 2 3 4 5 6 2'' 3'' 4'' 5'' 6'' 1'' 1' 6' 5' 4' 3' 2' 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 24 26 25 H_{α H} β 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

147 1 2 3 4 5 6 2'' 3'' 4'' 5'' 6'' 1'' 1' 6' 5' 4' 3' 2' 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 24 26 25 H_{α H} β 1_H-1_H-COSY 1_H-1_H-NOESY

147 1 2 3 4 5 6 2'' 3'' 4'' 5'' 6'' 1'' 1' 6' 5' 4' 3' 2' 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 26 25 H_{α H} β IR (KBr)

150 H_α H_β O O O 8 7 17 4 5 16 2 1 14 13 ₁₂ 11 10 9 15 3 6 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

150 H_α H_β O O O 8 7 17 4 5 16 2 1 14 13 ₁₂ 11 10 9 15 3 6 13_C-DEPT 1_H-1_H-COSY

150 H_α H_β O O O 8 7 17 4 5 16 2 1 14 13 ₁₂ 11 10 9 15 3 6 1_H-1_H-NOESY 1_H-13_C-HSQC

150 H_α H_β O O O 8 7 17 4 5 16 2 1 14 13 ₁₂ 11 10 9 15 3 6 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

150 H_α H_β O O O 8 7 17 4 5 16 2 1 14 13 ₁₂ 11 10 9 15 3 6 4 00 0,0 3 00 0 2 00 0 1 50 0 1 00 0 4 50 ,0 6 ,0 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0,8 cm-1 %T 3447 30643052 3030 2995 29602930 2908 2883 2860 19561917 18121735 1664 1602 1498 1475 1456 1447 1382 1366 1348 13071284 1246 1215 1195 11781156 1117 1099 1079 1054 1039₁₀₃₁ 979 960 942 926 910 891 869 841 826 810 760 745 722 701 678 652 630 575 504 471 IR (KBr)

151 O _O 1 2 3 ₄ 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 1' 1'' H_α Hβ 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

151 O _O 1 2 3 ₄ 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 1' 1'' Hα Hβ 1_H-1_H-COSY 1_H-1_H-NOESY

151 O _O 1 2 3 ₄ 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 1' 1'' Hα Hβ 1_H-13_C-HSQC 44 00,0 40 00 30 00 20 00 1500 10 00 450,0 8,2 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 39,9 cm-1 %T 4054,30 3448,30 3059,13 3030,85 2982,18 2961,98 2932,85 2914,19 2883,27 2834,28 1953,98 1909,96 1603,37 1498,69 1473,49 1457,00 1448,51 1357,11 1346,27 1306,84 1284,45 1265,79 1240,46 1174,26 1159,23 1114,26 1045,50 1021,31 979,96 937,13 921,82 897,41 876,85 847,71 753,99 745,80 729,17 698,81 677,68 663,83 638,40 596,04 533,18 501,86 IR (KBr)

MeOOC MeOOC O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17 16 154 1_{H-RMN (500 MHz, CDCl} 3) 13

MeOOC MeOOC O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17 16 154 13_C-DEPT 1_H-1_H-COSY

MeOOC MeOOC O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17 16 154 1_H-1_H-NOESY 1_H-13_C-HSQC

MeOOC MeOOC O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17 16 154 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

MeOOC MeOOC O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17 16 154 4 40 0,0 4 00 0 3 00 0 2 00 0 1 50 0 1 00 0 4 20 ,0 5 ,0 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 6,0 cm-1 %T 3437 3063 3025 2983 2942 2891 1967 1731 1603 1499 1477 1457 1448 1432 1351 1302 1272 1236 1217 1186 1160 1140 1113 1087 1076 1039 1024 979 955 942 928 914 795 765 744 734 699 668 660 556 498 480 IR (KBr)

155 O _N 1 _{2 3} 4 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 O O H_α Hβ 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

155 O _N 1 _{2 3} 4 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 O O H_α Hβ 13_C-DEPT 1_H-1_H-COSY

155 O _N 1 _{2 3} 4 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 O O H_α Hβ 1_H-1_H-NOESY 1_H-13_C-HSQC

155 O _N 1 _{2 3} 4 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 O O H_α Hβ 1_H-13_{C-HMBC J = 8 Hz} 1_H-13_{C-HMBC J = 5 Hz}

155 O _N 1 _{2 3} 4 5 6 7 8 9 10 11 12 13 14 15 ₁₆ 17 O O Hα H_β 4400,0 4000 3000 20 00 15 00 1000 450,0 8,2 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 39 ,9 cm-1 %T 4054,30 3448,30 3059,13 3030,85 2982,18 2961,98 2932,85 2914,19 2883,27 2834,28 1953,98 1909,96 1603,37 1498,69 1473,49 1457,00 1448,51 1357,11 1346,27 1306,84 1284,45 1265,79 1240,46 1174,26 1159,23 1114,26 1045,50 1021,31 979,96 937,13 921,82 897,41 876,85 847,71 753,99 745,80 729,17 698,81 677,68 663,83 638,40 596,04 533,18 501,86 IR (KBr)

157 S O O O O O 1 2 3 4 5 6 7 8 9 ₁₀ 11 12 13 14 15 16 17 Hα H_β 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl )}

157 S O O O O O 1 2 3 4 5 6 7 8 9 ₁₀ 11 12 13 14 15 16 17 Hα H_β 13_C-DEPT 1_H-1_H-NOESY

157 S O O O O O 1 2 3 4 5 6 7 8 9 ₁₀ 11 12 13 14 15 16 17 Hα H_β IR (KBr)

158 S O O O O 12 11 10 9 25 6 726 ₄ 3 2 1 24 21 20 19 13 14 15 16 17 18 8 5 Hα _H β 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

158 S O O O O 12 11 10 9 25 6 726 ₄ 3 2 1 24 21 20 19 13 14 15 16 17 18 8 5 Hα _H β 1_H-1_H-NOESY 1_H-13_C-HSQC

158 S O O O O 12 11 10 9 25 6 726 ₄ 3 2 1 24 21 20 19 13 14 15 16 17 18 8 5 Hα _H β IR (KBr)

H H 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 162 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

H H 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 162 1_H-1_H-COSY IR (KBr)

I H 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 167 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

I H 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 167 1_H-1_H-COSY 1_H-1_H-NOESY

I H 1 3 4 5 6 7 8 1'' 2'' 3'' 4'' 5'' 6'' 1' 2' 6' 167 1_H-13_C-HSQC IR (KBr)

177

1_{H-RMN (500 MHz, CDCl} 3)

13_{C-RMN (100.6 MHz, CDCl} 3)

177

1_H-1_H-NOESY

177

180 O O 5 ₆ 7 8 9 10 13 14 15 16 1_{H-RMN (500 MHz, CDCl} 3) a 25ºC 13_{C-RMN (75.4 MHz, CDCl} 3)

180 O O 5 ₆ 7 8 9 10 13 14 15 16 13_C-DEPT 1_H-13_{C-HSQC a 25ºC}

180 O O 5 ₆ 7 8 9 10 13 14 15 16 1_{H-RMN (500 MHz, CDCl} 3) a 10ºC 1_{H-RMN (500 MHz, CDCl} 3) a 0ºC

180 O O 5 ₆ 7 8 9 10 13 14 15 16 1_H-13_{C-HSQC a 0ºC} 1_{H-RMN (500 MHz, CDCl} 3) a 40 ºC

180 O O 5 ₆ 7 8 9 10 13 14 15 16 1_{H-RMN (500 MHz, CDCl} 3) a 50ºC 1_H-13_{C-HSQC a 50ºC}

180 O O 5 ₆ 7 8 9 10 13 14 15 16 4 00 0,0 3 00 0 2 00 0 1 50 0 1 00 0 4 50 ,0 8 ,0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 7,0 cm-1 %T 3422 2986 2968 2941 2914 2864 2833 2363 1648 1448 1378 1370 1364 1319 1296 1259 12391192 1151 1126 1081 1069 1033 924 872 864 847 797 721 668 619 530 509 IR (KBr)

O O 5 6 7 8 9 10 13 14 15 16 181 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

O O 5 6 7 8 9 10 13 14 15 16 181 13_C-DEPT 1_H-1_H-NOESY

O O 5 6 7 8 9 10 13 14 15 16 181 4 00 0,0 3 00 0 2 00 0 1 50 0 1 00 0 4 50 ,0 7 ,0 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 6 8,0 cm-1 %T 3421,87 2977,15 2964,12 2932,28 2914,77 2890,63 2858,04 2836,64 2824,66 2717,25 2658,84 1938,71 1699,70 1479,82 1451,68 1363,56 1270,09 1246,09 1176,03 1138,58 1116,33 1083,44 1031,12 982,21 936,42 920,17 762,02 710,90 585,63 525,59 457,81 IR (KBr)

I 193 4 ₅ 6 7 8 NH2 O 1_{H-RMN (300 MHz, DMSO-d} 6) 13_{C-RMN (75.4 MHz, DMSO-d} 6)

I 193 4 ₅ 6 7 8 NH2 O 13_C-DEPT 4000,0 3000 2 00 0 1 50 0 1 00 0 4 50 ,0 20,0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 0 74,0 cm-1 %T 3477 3344 3000 2924 2581 1702 1630 1594 1477 1406 1310 1276 1238 1216 1172 1135 1097 994 963 817 760 722 571 493 464 IR (KBr)

H O 201 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

H O

201

13_C-DEPT

H O

201

1_H-1_H-NOESY

H O

201

1_H-13_{C-HMBC J = 8 Hz}

H O 201 4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450,0 67,5 70 75 80 85 90 95 100 105 110 115 120 125,0 cm-1 %T 3343 3072 2963 2872 1698 1643 1538 1479 1409 1366 1270 1199 1158 1086 963 902 873 784 648 551 IR (NaCl)

H O 200 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

H O

200

13_C-DEPT

H O

200

1_H-1_H-NOESY

H O

200

1_H-13_{C-HMBC J = 8 Hz}

H O 200 4 40 0,0 4000 3 00 0 2 00 0 1 500 1 00 0 4 50 ,0 2 0,0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 2,0 cm-1 %T 3409 3088 2970 2871 1693 1661 1533 1478 1464 1412 1392 1366 1323 1282 1261 1235 1187 1161 1092 1078 988 924 894 786 754 574 527 IR (KBr)

I 197 4 ₅ 6 7 8 NHMe O 1_{H-RMN (300 MHz, CD} 3OD) 13_{C-RMN (75.4 MHz, CD} 3OD)

I 197 4 ₅ 6 7 8 NHMe O 13_C-DEPT 4400,0 4 000 300 0 2000 1 500 100 0 450,0 1 3,0 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 2,0 cm-1 %T 3373 2943 2624 1696 1627 1612 1549 1474 1420 1330 1292 1248 1219 1160 1110 1072 991 960 904 819 743 710 657 640 603 554 476 IR (KBr)

137 O O 1 2 3 ₄ 5 6 7 8 9 10 11 12 13 14 1516 1' 1'' 1'' 1' 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

137 O O 1 2 3 ₄ 5 6 7 8 9 10 11 12 13 14 1516 1' 1'' 1'' 1' 13_C-DEPT cinética de 1H a 45ºC

137 O O 1 2 3 ₄ 5 6 7 8 9 10 11 12 13 14 1516 1' 1'' 1'' 1' cinética de 1H a 50ºC

O O O 218 1 2 ₄ 5 6 7 8 9 10 11 13 14 ₁₅ 16 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

O O O 218 1 2 ₄ 5 6 7 8 9 10 11 13 14 ₁₅ 16 13_C-DEPT 4 00 0,0 3 00 0 2 00 0 1 50 0 1 00 0 4 50 ,0 1 0,0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 5 7,0 cm-1 %T 3430,30 2966,59 2934,00 2881,43 2855,20 2720,36 2669,15 1960,18 1742,31 1473,91 1463,79 1430,56 1364,18 1302,15 1290,90 1277,08 1207,55 1194,57 1178,53 1153,68 1131,89 1085,441040,92 990,88 971,29 952,01 924,64 898,12 718,48 693,88 662,12 544,10 526,01 468,90 IR (KBr)

220 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 Br 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl )}

220 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 Br 13_C-DEPT 1_H-1_H-COSY

220 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 Br 1_H-1_H-NOESY 1_H-13_C-HSQC

220 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 Br 1_H-13_{C-HMBC J = 8 Hz} 4400,0 4000 3000 2000 1500 1000 450,0 30,5 35 40 45 50 55 60 65 70 75 78,8 cm-1 %T 3431 2958 2920 2874 2841 2364 1718 1459 1359 1306 1267 1237 1176 1103 1089 1028 979 951 924 910 857 739 723 659 IR (KBr)

219 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 I 1_{H-RMN (500 MHz, CDCl} 3) 13_{C-RMN (100.6 MHz, CDCl} 3)

219 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 I 13_C-DEPT 1_H-1_H-COSY

219 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 I 1_H-1_H-NOESY 1_H-13_C-HSQC

219 O O 2 3 ₄ 5 6 7 8 9 10 11 13 16 15 14 I 1_H-13_{C-HMBC J = 8Hz} 4400,0 4000 3000 2000 1500 1000 450,0 27,0 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68,0 cm-1 %T 3434 2971 2946 2845 1466 1455 1355 1304 1259 1237 1189 1171 1103 1081 1060 1028 991 975 949 918 906 854 731 724 653 465 IR (KBr)

136 O 5 6 O 7 8 9 10 13 14 15 16 1_{H-RMN (300 MHz, CDCl} 3) 13_{C-RMN (75.4 MHz, CDCl} 3)

136 O 5 6 O 7 8 9 10 13 14 15 16 13_C-DEPT 4 00 0,0 300 0 2 000 1 50 0 1 00 0 450 ,0 2 0,0 25 30 35 40 45 50 55 60 65 7 1,0 cm-1 %T 3435 2986 2966 2954 2924 2878 2729 1578 1473 1443 13791366 1289 1274 1247 1214 1178 1156 1127 1080 1072 1035 1013 921 842 806 728 667 622 569505 IR (KBr)

204 HO 5 6 OH 7 8 9 10 13 14 15 16 1_{H-RMN (300 MHz, DMSO-d} 6) 13_{C-RMN (75.4 MHz, DMSO} 6)

204 HO 5 6 OH 7 8 9 10 13 14 15 16 13_C-DEPT 4 00 0,0 3000 2 000 1 50 0 1000 450,0 40,0 45 50 55 60 65 70 75,0 cm-1 %T 3269 2956 2929 2880 1640 1474 1276 1219 1178 1118 1077 1029 747 IR (KBr)

205 HO 5 6 OH 7 8 9 10 13 14 15 16 1_{H-RMN (300 MHz, DMSO-d} 6) 13_{C-RMN (75.4 MHz, DMSO} 6)

205 HO 5 6 OH 7 8 9 10 13 14 15 16 13_C-DEPT 44 00,0 40 00 30 00 20 00 15 00 10 00 45 0,0 6,4 8 10 12 14 16 18 20 22 24 26 28 ,0 cm-1 %T DIM-TOH 3270,4 2979,4 2960,0 2896,7 2852,0 2833,8 1450,6 1329,8 1313,3 1299,4 1269,1 1239,9 1200,1 1173,2 1133,8 1070,6 1039,8 1023,2 961,5 863,6 812,9 726,7 692,7 548,2 IR (KBr)

Anexo 2.

R-X de endo,endo-105. MeOOC COOMe 1 2 3 4 5 6 7 8 1' 2' _3' 4' 5' 6' 1'' 2'' 3'' 4'' 5'' 6''