Beta-Aminoisobutyric Acid → Cryptophycin 21

HRID 849807

Reaktionsgleichung

Reaktionsgleichung von HRID 849807
[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]=[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](C)[C:39]([OH:41])=[O:40].[C:43](O)(=[O:50])[CH:44]([CH2:46][CH:47]([CH3:49])[CH3:48])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>[CH3:20][C@H:9]([C@H:10]1[O:19][C@@H:11]1[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[C@H:2]1[O:1][C:43](=[O:50])[C@H:44]([CH2:46][CH:47]([CH3:49])[CH3:48])[O:41][C:39](=[O:40])[CH2:38][CH2:37][NH:36][C:28](=[O:30])[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)[NH:27][C:6](=[O:8])[CH:5]=[CH:4][CH2:3]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 538202503-Chloro-O-methyl-L-tyrosineHCID 540066555,7,8-Trihydroxy-6-methyl-8-phenyl-2-octenoic acidHCID 101025283Cryptophycin 43×

Produkt 1

HCID 10508360Cryptophycin 21

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

[α]D +41.3° (MeOH, c 5.2); UV λmax (ε) 242 (4963), 280 (2430), 286 (2212); IR (neat) νmax 3402, 3270, 2960, 1748, 1724, 1676, 1514, 1466, 1343, 1239, 1177 cm-1 ; EIMS m/z (rel intensity) 640/642 (66/27), 398/400 (47/16), 265 (55), 227 (93), 181 (100); high resolution EIMS m/z 640.25676 (calcd for C34H41ClN2O8, -1.6 mmu error). 1H NMR (CDCl3): amino or hydroxyacid unit δ (carbon position, multiplicity; J in Hz) 7,8-epoxy-5-hydroxy-6-methyl-8-phenyl-2-octenoic acid (A) 5.74 (2, d; 16), 6.67 (3, ddd; 15.3, 9.7 and 5.5), 2.45 (4, dt; 14.3 and 10.4), 2.55 (4, brdd; 14.3 and 5.3), 5.15 (5, ddd; 11.2, 4.8 and 1.8), 1.8 (6, m), 1.14 (6-Me, d; 7.0), 2.92 (7, dd; 7.5 and 2.0), 3.69 (8, d; 2.0), 7.24-7.26 (10/14, m), 7.33-7.39 (11/12/13, m); 3-chloro-4-hydroxyphenylalanine (B) 4.8 (2, m), 5.64 (2-NH, d; 8.8), 3.03 (3, dd; 14.5 and 7.0), 3.11 (3, dd; 14.4 and 5.6), 7.17 (5, d; 2.2), 5.61 (7-OH), s), 6.91 (8, d; 8.3), 7.0 (9, dd; 8.3 and 2.2); 3-amino-2-methylpropionic acid (C) 2.71 (2, m), 1.22 (2-Me, d; 7.3), 3.28 (3, dt; 13.6 and 6.8), 3.49 (3, ddd; 13.6, 5 and 4.1), 6.92 (3-NH, br t; 6.1) leucic acid (D) 4.83 (2, dd; 10.1 and 3.3), 1.36 (3, m), 1.67-1.75 (3, m), 1.67-1.75 (4, m), 0.85 (5, d; 7.5), 0.86 (5', d; 6.8). 13C NMR (CDCl3) unit δ (carbon position) A 165.3 (1), 125.3 (2), 141.0 (3), 36.7 (4), 76.2 (5), 40.6 (13.5 (6-Me), 63.0 (7), 59.0 (8), 136.8 (9), 125.6 (10/14), 128.7 (11/13), 128.6 (12); B 170.9 (1), 53.6 (2), 35.1 (3), 129.9 (4), 129.6 (5), 120.0 (6), 150.4 (7), 116.4 (8), 129.2 (9); C 175.6 (1), 38.3 (2), 14.1 (2-Me), 41.1 (3); D 170.8 (1), 71.3 (2), 39.4 (3), 24.6 (4), 21.3 (5), 22.9 (5').

Quellen und Nachweise

ORD-Eintrag
ord-9bef4e47da5541cebe4c0fc6c55e5b94
Quelldatensatz
uspto-grants-2000_01
Patentnummer
US06013626

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