N-(tert-butoxycarbonyl)glycine → tert-butyl[2-(2-{(3E)-4-[3-methyl-4-({5-(propan-2-yl)-3-[(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)oxy]-1H-pyrazol-4-yl}methyl)phenyl]but-3-en-1-yl}-2,9-diazaspiro[5.5]undec-9-yl)-2-oxoethyl]carbamate

HRID 1625942Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1625942
F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2N=CC=CC=2N=N1.Cl.Cl.[C:27]([O:30][C@@H:31]1[C@@H:68]([O:69][C:70](=[O:72])[CH3:71])[C@H:67]([O:73][C:74](=[O:76])[CH3:75])[C@@H:66]([CH2:77][O:78][C:79](=[O:81])[CH3:80])[O:65][C@H:32]1[O:33][C:34]1[C:38]([CH2:39][C:40]2[CH:45]=[CH:44][C:43](/[CH:46]=[CH:47]/[CH2:48][CH2:49][N:50]3[CH2:55][CH2:54][CH2:53][C:52]4([CH2:60][CH2:59][NH:58][CH2:57][CH2:56]4)[CH2:51]3)=[CH:42][C:41]=2[CH3:61])=[C:37]([CH:62]([CH3:64])[CH3:63])[NH:36][N:35]=1)(=[O:29])[CH3:28].[CH3:82][C:83]([O:86][C:87]([NH:89][CH2:90][C:91](O)=[O:92])=[O:88])([CH3:85])[CH3:84].C(N(C(C)C)CC)(C)C>ClCCl>[C:83]([O:86][C:87](=[O:88])[NH:89][CH2:90][C:91]([N:58]1[CH2:57][CH2:56][C:52]2([CH2:51][N:50]([CH2:49][CH2:48]/[CH:47]=[CH:46]/[C:43]3[CH:44]=[CH:45][C:40]([CH2:39][C:38]4[C:34]([O:33][C@@H:32]5[O:65][C@H:66]([CH2:77][O:78][C:79](=[O:81])[CH3:80])[C@@H:67]([O:73][C:74](=[O:76])[CH3:75])[C@H:68]([O:69][C:70](=[O:72])[CH3:71])[C@H:31]5[O:30][C:27](=[O:29])[CH3:28])=[N:35][NH:36][C:37]=4[CH:62]([CH3:64])[CH3:63])=[C:41]([CH3:61])[CH:42]=3)[CH2:55][CH2:54][CH2:53]2)[CH2:60][CH2:59]1)=[O:92])([CH3:85])([CH3:82])[CH3:84]

Komponenten

6

Edukt 4

HCID 78288N-(tert-butoxycarbonyl)glycineHCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 867208844-{4-[(1E)-4-(2,9-diazaspiro[5.5]undec-2-yl)but-1-en-1-yl]-2-methylbenzyl}-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside dihydrochloride

Produkt 1

HCID 131731669tert-butyl[2-(2-{(3E)-4-[3-methyl-4-({5-(propan-2-yl)-3-[(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)oxy]-1H-pyrazol-4-yl}methyl)phenyl]but-3-en-1-yl}-2,9-diazaspiro[5.5]undec-9-yl)-2-oxoethyl]carbamateAusbeute 90,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

Add O-(7-azabenzotriazol-1-yl)-N,N,N′,N′ tetramethyluronium hexafluorophosphate (HATU, 543 mg, 1.43 mmol) to a solution of 4-{4-[(1E)-4-(2,9-diazaspiro[5.5]undec-2-yl)but-1-en-1-yl]-2-methylbenzyl}-5-(propan-2-yl)-1H-pyrazol-3-yl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside dihydrochloride (1.0 g, 1.19 mmol), N-alpha-T-Boc-glycine (317 mg, 1.79 mmol), and diisopropylethylamine (769 mg, 5.95 mmol) in dichloromethane (10 mL). Stir the mixture at room temperature for 2.0 hours. Remove the solvent under the reduced pressure. Purify the resulting residue by flash chromatography (silica gel, gradient ethyl acetate/dichloromethane from 30-85% over 20 min, 40 g column) to provide the title compound (1.0 g, 1.08 mmol). MS (m/z): 924.4 (M+1), 922.4 (M−1).

Aufarbeitung

  1. customRemove the solvent under the reduced pressure
  2. customPurify the resulting residue by flash chromatography (silica gel, gradient ethyl acetate/dichloromethane from 30-85% over 20 min, 40 g column)

Quellen und Nachweise

ORD-Eintrag
ord-fb02ebd28cf74446b1549b7b2a40d581
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08785404B2

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