Beta-Aminoisobutyric Acid → Cryptophycin 31

HRID 618582

Reaktionsgleichung

Reaktionsgleichung von HRID 618582
[OH:1][CH:2]([CH:9]([CH3:20])[CH:10]([OH:19])[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]=[C:32]([Cl:36])[C:33]=1[O:34][CH3:35])[CH2:25][C@@H:26]([C:28]([OH:30])=O)[NH2:27].[NH2:37][CH2:38][CH:39]([CH3:43])[C:40]([OH:42])=[O:41].[C:44](O)(=[O:51])[CH:45]([CH2:47][CH:48]([CH3:50])[CH3:49])O.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>[CH3:43][C@H:39]1[C:40](=[O:42])[O:41][C@@H:45]([CH2:47][CH:48]([CH3:50])[CH3:49])[C:44](=[O:51])[O:1][C@H:2]([C@@H:9]([C@H:10]2[O:19][C@@H:11]2[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=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]=[C:32]([Cl:36])[C:33]([O:34][CH3:35])=[C:22]([Cl:21])[CH:23]=2)[C:28](=[O:30])[NH:37][CH2:38]1

Komponenten

11

Edukt 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×HCID 6438401Cryptophycin4×HCID 9985532Cryptophycin 6HCID 10077879Cryptophycin 34×HCID 540066555,7,8-Trihydroxy-6-methyl-8-phenyl-2-octenoic acidHCID 545644093,5-Dichloro-4-methoxyphenylalanineHCID 101025283Cryptophycin 43×

Produkt 1

HCID 10556556Cryptophycin 31

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

[α]D +50.6°(MeOH, c 1.13); UV λmax (ε) 242 (3800), 284 (700); IR (neat) νmax 3412, 3272, 2961, 1745, 1725, 1678, 1537, 1481, 1270, 1196, 1176, 1000, 698 cm-1 ; EIMS m/z (rel intensity) 688/690/692 (1.2/1.0/0.4), 446/448/450 (7.9/6.7/3.1), 314/316/318 (17/11/3), 91 (100); high resolution EIMS m/z 688.2336 (calcd for C35H42Cl2N2O8, -1.8 mmu error); 1H-NMR (CDCl3)amino or hydroxy acid unit δ (carbon position, multiplicity; J in Hz) 7,8-epoxy-5-hydroxy-6-methyl-8-phenyl-2-octenoic acid (A) 5.78 (2, d; 15.5), 6.66 (3, ddd; 15.5, 9.4 and 6.0), 2.47 (4, ddd; 14.1, 10.8 and 9.4), 2.56 (4, m), 5.14 (5, ddd; 10.8, 4.7 and 1.7), 1.82 (6, m), 1.15 (6-Me, d; 7.1), 2.93 (7, dd; 7.5 and 1.9), 3.70 (8, d; 1.9), 7.24-7.26 (10/14, m), 7.34-7.39 (11/12/13, m); 3,5-dichloro-4-methoxyphenylalanine (B) 4.83 (2, m), 5.68 (2-NH, d; 9.0), 3.0 (3, dd; 14.4 and 7.3), 3.14 (3, dd; 14.4 and 5.6), 7.16 (5/9, s), 3.87 (7-OMe, s); 3-amino-2-methylpropionic acid (C) 2.74 (2, m), 1.22 (2-Me, d; 7.1), 3.20 (3, m), 3.58 (3, ddd; 13.5, 5.6 and 4.1), 6.82 (3-NH, br t; 5.6); leucic acid (D) 4.83 (2, m), 1.38 (3, m), 1.72 (3, m), 1.72 (4, m). 0.87 (4-Me, d; 6.8), 0.86 (5, d; 6.8); 13C NMR (CDCl3) unit δ (carbon position) A 165.4 (1), 125.4 (2), 141.0 (3), 36.7 (4), 76.3 (5), 40.6 (6), 13.5 (6-Me), 63.0 (7), 58.9 (8), 136.7 (9), 125.6 (10/14), 128.7 (11/13), 128.6 (12); B 170.8 (1), 53.3 (2), 35.2 (3), 129.3 (4), 129.6 (5/9), 134.5 (6/8), 151.2 (7), 60.6 (7-OMe); C 175.3 (1), 38.3 (2), 13.9 (2-CH3), 41.5 (3), D 170.6 (1), 71.3 (2), 39.4 (3), 24.6 (4), 22.9 (4-Me), 21.3 (5).

Quellen und Nachweise

ORD-Eintrag
ord-fb4e452bbb0c4bc7a121e806cb6e5531
Quelldatensatz
uspto-grants-1999_09
Patentnummer
US05952298

Verknüpfte Notizen

Wird geladen…