Beta-Aminoisobutyric Acid → Cryptophycin 19

HRID 618577

反応式

HRID 618577 の反応式
[OH:1][CH:2]([CH:9]([CH3:20])[CH:10](O)[CH:11](O)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:3][CH:4]=[CH:5][C:6]([OH:8])=O.[Cl:21][C:22]1[CH:23]=[C:24]([CH:31]=[CH:32][C:33]=1[O:34][CH3:35])[CH2:25][C@@H:26]([C:28]([OH:30])=O)[NH2:27].[NH2:36][CH2:37][CH:38]([CH3:42])[C:39]([OH:41])=[O:40].C(O)(=O)[CH:44]([CH2:46][CH:47]([CH3:49])[CH3:48])[OH:45].C[C@H]1C(=O)O[C@@H](CC(C)C)C(=O)O[C@H]([C@@H]([C@H]2O[C@@H]2C2C=CC=CC=2)C)CC=CC(=O)N[C@H](CC2C=CC(OC)=C(Cl)C=2)C(=O)NC1.CC1C(=O)OC(CC(C)C)C(=O)OC(C(C2OC2C2C=CC=CC=2)C)CC=CC(=O)NC(CC2C=CC(OC)=C(Cl)C=2)C(=O)NC1.C[C@H]1C(=O)O[C@@H](CC(C)C)C(=O)O[C@H]([C@@H](/C=C/C2C=CC=CC=2)C)CC=CC(=O)N[C@H](CC2C=CC(OC)=C(Cl)C=2)C(=O)NC1.C[C@H]1C(=O)O[C@@H](CC(C)C)C(=O)O[C@H]([C@@H](/C=C/C2C=CC=CC=2)C)CC=CC(=O)N[C@H](CC2C=CC(OC)=CC=2)C(=O)NC1.C[C@@H]1[C@@H](O)[C@H](C2C=CC=CC=2)O[C@H]1C/C=C/C(N[C@@H](C(NC[C@H](C(OC)=O)C)=O)CC1C=CC(OC)=C(Cl)C=1)=O>CO>[CH3:42][C@H:38]1[C:39](=[O:41])[O:40][C@@H:46]([CH:47]([CH3:49])[CH3:48])[C:44](=[O:45])[O:1][C@H:2]([C@@H:9](/[CH:10]=[CH:11]/[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH3:20])[CH2:3][CH:4]=[CH:5][C:6](=[O:8])[NH:27][C@H:26]([CH2:25][C:24]2[CH:31]=[CH:32][C:33]([O:34][CH3:35])=[C:22]([Cl:21])[CH:23]=2)[C:28](=[O:30])[NH:36][CH2:37]1

参加物

11

反応物 9

HCID 64956Beta-Aminoisobutyric AcidHCID 92779(+-)-2-Hydroxyisocaproic acidHCID 5468287(13E)-10-[(3-chloro-4-methoxyphenyl)methyl]-6-methyl-3-(2-methylpropyl)-16-[1-(3-phenyloxiran-2-yl)ethyl]-1,4-dioxa-8,11-diazacyclohexadec-13-ene-2,5,9,12-tetrone6 回HCID 6438401Cryptophycin4 回HCID 9985532Cryptophycin 62 回HCID 10077879Cryptophycin 34 回HCID 538202503-Chloro-O-methyl-L-tyrosineHCID 540066555,7,8-Trihydroxy-6-methyl-8-phenyl-2-octenoic acidHCID 101025283Cryptophycin 43 回

生成物 1

HCID 10555920Cryptophycin 19

試薬・触媒・溶媒 1

HCID 887Methanol溶媒2 回

実験手順

[α]D +62.6°(MeOH, c 0.67); UV (MeOH) λmax (ε) 204 (44900), 230 (17000), 248 (15600), 280 (2500); IR (neat) νmax 3413, 3272, 2966, 1745, 1726, 1672, 1504, 1258, 1199, 1178, 1066, 692 cm-1 ; EIMS m/z (rel intensity) 624/626 (3.0/1.4), 398/400 (58/21), 280/282(15/5), 227 (100), 195/197 (57/22); high resolution EIMS m/z 624.2585 (calcd for C34H41ClN2O7, 1.8 mmu error). 1H-NMR (CDCl3):amino or hydroxy acid unit δ (carbon position, multiplicity; J in Hz) 5-hydroxy-6-methyl-8-phenyl-2,7-octadienoic acid (A) 5.76 (2, d; 15.2), 6.64 (3, ddd; 15.4, 9.1 and 6.2), 2.38 (4, m), 2.47 (4, m), 5.04 (5, ddd;7.1, 5.1 and 1.8), 2.57 (6, m), 1.15 (6-Me, d; 6.9), 6.05 (7, dd; 15.8 and 8.5), 6.43 (8, d; 15.8), 7.29-7.35 (10/11/13/14, m), 7.23 (12, m); 3-chloro-4-methoxyphenylalanine (B) 4.84 (2, m), 5.67 (2-NH, d; 8.9), 3.04(3, dd; 14.3 and 7.1), 3.14 (3, dd; 14.3 and 5.3), 7.22 (5, d; 2.0), 3.86 (7-OCH3, s), 6.83 (8, d; 8.2), 7.08 (9, dd; 8.2 and 2.0); 3-amino-2-methylpropionic acid (C) 2.75 (2, m), 1.23 (2-Me, d; 7.1), 3.19 (3, m), 3.59 (3, m), 6.80 (3-NH, brt; 6.7); 2-hydroxyisovaleric acid (D) 4.73 (2, d; 4.2), 2.09 (3, m), 0.84 (4, d; 6.9), 0.95 (4', d; 6.9). 13C NMR (CDCl3) unit δ (carbon position) A 165.5 (1), 125.3 (2), 141.3 (3), 36.3 (4), 77.7 (5), 42.0 (6), 17.1 (6-Me), 129.9 (7), 131.9 (8), 136.8 (9), 126.1 (10/14), 128.6 (11/13), 127.6 (12); B 171.0 (1), 53.4 (2), 35.1 (3), 130.0 (4), 131.1 (5), 122.4 (6), 153.9 (7), 56.1 (7-OMe), 112.2 (8), 128.5 (9); C 175.1 (1), 38.7 (2), 13.9 (2-Me), 41.5 (3), D 169.6 (1), 76.9 (2), 29.8 (3), 19.0 (4), 16.7 (3-Me).

出典と根拠

ORDレコード
ord-bb59bd60274a484fbd54df2f113a3169
出典データセット
uspto-grants-1999_09
特許番号
US05952298

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