StartseiteMCPWorkbenchSkills
StartseiteWorkbenchBenachrichtigungenMein Bereich
llms.txt · MCP-AnleitungDatenschutz · Nutzungsbedingungen · Supportv1.8.0
  1. Startseite
  2. /Reaktion

Dicyclohexylcarbodiimide → t-Butyldimethylsilyl 6-O-{3-O-allyloxycarbonyl-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3yl)-2-[(R)-3-dodecanoyloxy-tetradecanoylamino]-beta-D-glucopyranosyl}-2-azido-4-O-benzyl-3-O-[(R)-3-benzyloxy-tetradecanoyl]-2-deoxy-beta-D-glucopyranoside

HRID 628193
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 628193
[CH2:1]([O:8][C@H:9]([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:10][C:11]([OH:13])=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1CCC(N=C=NC2CCCCC2)CC1.[CH2:40]([O:43][C:44]([O:46][C@H:47]1[C@H:52]([O:53][P:54]2(=[O:65])[O:60][CH2:59][C:58]3[CH:61]=[CH:62][CH:63]=[CH:64][C:57]=3[CH2:56][O:55]2)[C@@H:51]([CH2:66][O:67][CH2:68][C:69]2[CH:74]=[CH:73][CH:72]=[CH:71][CH:70]=2)[O:50][C@@H:49]([O:75][CH2:76][C@H:77]2[O:90][C@@H:81]([O:82][Si:83]([C:86]([CH3:89])([CH3:88])[CH3:87])([CH3:85])[CH3:84])[C@H:80]([N:91]=[N+:92]=[N-:93])[C@@H:79](O)[C@@H:78]2[O:95][CH2:96][C:97]2[CH:102]=[CH:101][CH:100]=[CH:99][CH:98]=2)[C@@H:48]1[NH:103][C:104](=[O:132])[CH2:105][C@H:106]([O:118][C:119](=[O:131])[CH2:120][CH2:121][CH2:122][CH2:123][CH2:124][CH2:125][CH2:126][CH2:127][CH2:128][CH2:129][CH3:130])[CH2:107][CH2:108][CH2:109][CH2:110][CH2:111][CH2:112][CH2:113][CH2:114][CH2:115][CH2:116][CH3:117])=[O:45])[CH:41]=[CH2:42]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH2:40]([O:43][C:44]([O:46][C@H:47]1[C@H:52]([O:53][P:54]2(=[O:65])[O:60][CH2:59][C:58]3[CH:61]=[CH:62][CH:63]=[CH:64][C:57]=3[CH2:56][O:55]2)[C@@H:51]([CH2:66][O:67][CH2:68][C:69]2[CH:70]=[CH:71][CH:72]=[CH:73][CH:74]=2)[O:50][C@@H:49]([O:75][CH2:76][C@H:77]2[O:90][C@@H:81]([O:82][Si:83]([C:86]([CH3:87])([CH3:89])[CH3:88])([CH3:84])[CH3:85])[C@H:80]([N:91]=[N+:92]=[N-:93])[C@@H:79]([O:12][C:11](=[O:13])[CH2:10][C@H:9]([O:8][CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[C@@H:78]2[O:95][CH2:96][C:97]2[CH:98]=[CH:99][CH:100]=[CH:101][CH:102]=2)[C@@H:48]1[NH:103][C:104](=[O:132])[CH2:105][C@H:106]([O:118][C:119](=[O:131])[CH2:120][CH2:121][CH2:122][CH2:123][CH2:124][CH2:125][CH2:126][CH2:127][CH2:128][CH2:129][CH3:130])[CH2:107][CH2:108][CH2:109][CH2:110][CH2:111][CH2:112][CH2:113][CH2:114][CH2:115][CH2:116][CH3:117])=[O:45])[CH:41]=[CH2:42]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 10868DicyclohexylcarbodiimideHCID 11110428(R)-3-(Benzyloxy)tetradecanoic acidHCID 16216230t-Butyldimethylsilyl 6-O-{3-O-allyloxycarbonyl-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3yl)-2-[(R)-3-dodecanoyloxy-tetradecanoylamino]-beta-D-glucopyranosyl}-2-azido-4-O-benzyl-2-deoxy-beta-D-glucopyranoside

Produkt 1

HCID 16216359
t-Butyldimethylsilyl 6-O-{3-O-allyloxycarbonyl-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3yl)-2-[(R)-3-dodecanoyloxy-tetradecanoylamino]-beta-D-glucopyranosyl}-2-azido-4-O-benzyl-3-O-[(R)-3-benzyloxy-tetradecanoyl]-2-deoxy-beta-D-glucopyranoside
Ausbeute 86 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

A reaction mixture of (R)-3-benzyloxy-tetradecanoic acid 15 (100 mg, 0.293 mmol) and DCC (93 mg, 0.450 mmol) in DCM (5 mL) was stirred at room temperature for 10 min, and then disaccharide 21 (300 mg, 0.225 mmol) in DCM (3 mL) and DMAP (11 mg, 0.090 mmol) were added. The reaction mixture was stirred at room temperature for 14 h, after which the solids were removed by filtration, and the residue washed with DCM (2×1 mL). The combined filtrates were concentrated in vacuo, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1, v/v) to give 22 as a white solid (319 mg, 86%). Rf=0.41 (hexane/ethyl acetate, 2/1, v/v). [α]26D=−2.8° (c=1.0, CHCl3). 1H NMR (500 MHz, CDCl3): δ 7.33-7.15 (m, 19H, aromatic), 5.94-5.85 (m, 2H, NH, OCH2CH═CH2), 5.45 (t, 1H, J2′,3′=J3′,4′=9.5 Hz, H-3′), 5.34 (d, 1H, J=17.5 Hz, OCH2CH═CH2), 5.22 (d, 1H, J=10.0 Hz, OCH2CH═CH2), 5.08-4.95 (m, 7H, H-1, H-3, H-3L, C6H4(CH2O)2P), 4.61-4.44 (m, 10H, H-1, H-4′, 3×CH2Ph, OCH2CH═CH2), 3.96 (d, 1H, J6′a,6′b=10.5 Hz, H-6′a), 3.88-3.85 (m, 1H, H-3S), 3.80 (d, 1H, J6a,6b=9.5 Hz, H-6a), 3.72-3.66 (m, 3H, H-5′, H-6b, H-6′b), 3.55-3.52 (m, 2H, H-4, H-5), 3.47-3.41 (m, 1H, H-2′), 3.27 (dd, 1H, J1,2=7.5 Hz, J2,3=10.0 Hz, H-2), 2.56 (dd, 1H, J2Sa,2Sb=16.0 Hz, J2Sa,3S=7.0 Hz, H-2Sa), 2.43 (dd, 1H, J2Sa,2Sb=16.0 Hz, J2Sb,3S=7.0 Hz, H-2Sb), 2.35 (dd, 1H, J2La,2Lb=15.0 Hz, J2La,3L=6.0 Hz, H-2La), 2.30-2.20 (m, 3H, H-2L′, H-2L′b), 1.59-1.52 (m, 6H, H-4L, H-4S, H-3L′), 1.23 (broad, 52H, 26×CH2, lipid), 0.90 (s, 9H, SiC(CH3)3), 0.88-0.84 (m, 9H, 3×CH3, lipid), 0.12 (s, 6H, Si(CH3)2). 13C NMR (75 MHz, CDCl3): δ 173.40 (C═O), 170.55 (C═O), 169.94 (C═O), 154.42 (C═O), 138.46-127.35 (aromatic, OCH2CH═CH2), 118.74 (OCH2CH═CH2), 99.29 (C-1′), 96.96 (C-1), 75.89, 75.62, 74.75, 74.28, 74.02, 73.67, 73.41, 71.34, 70.89, 68.87-67.85 (m), 66.48, −4.18 (Si(CH3)2), −5.38 (Si(CH3)2). HR MS (m/z) calculated for C91H139N4O19Psi[M+Na]+, 1673.9438. found, 1674.1754.

Aufarbeitung

  1. stirringThe reaction mixture was stirred at room temperature for 14 h
  2. customafter which the solids were removed by filtration
  3. washthe residue washed with DCM (2×1 mL)
  4. concentrationThe combined filtrates were concentrated in vacuo
  5. customthe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1

Quellen und Nachweise

ORD-Eintrag
ord-9aa614a2fc164cefaa96d247f5fd6841
Quelldatensatz
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09309276B2

Notizen zur Reaktion

Wird geladen…

Auf dieser SeiteKomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion