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Triphenylphosphine → allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methyl-2-(1-methyl-2,2-dioxo-8-triethylsilanyloxymethyl-1,2-dihydro-2-thia-1,3-diaza-cyclopenta[alpha]naphthalen-3-ylmethyl)-carbapen-2-em-3-carboxylate

HRID 1596731
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1596731
[CH2:1]([O:4][C:5]([O:7][C@@H:8]([C@H:10]1[C:25](=[O:26])[N:12]2[C:13]([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])=[C:14]([CH2:17]O)[C@H:15]([CH3:16])[C@H:11]12)[CH3:9])=[O:6])[CH:2]=[CH2:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:46][N:47]1[C:51]2=[C:52]3[C:57](=[CH:58][CH:59]=[C:50]2[NH:49][S:48]1(=[O:70])=[O:69])[CH:56]=[CH:55][C:54]([CH2:60][O:61][Si:62]([CH2:67][CH3:68])([CH2:65][CH3:66])[CH2:63][CH3:64])=[CH:53]3.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.C(Cl)(Cl)Cl>[CH2:1]([O:4][C:5]([O:7][C@@H:8]([C@H:10]1[C:25](=[O:26])[N:12]2[C:13]([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])=[C:14]([CH2:17][N:49]3[C:50]4=[CH:59][CH:58]=[C:57]5[C:52]([CH:53]=[C:54]([CH2:60][O:61][Si:62]([CH2:67][CH3:68])([CH2:63][CH3:64])[CH2:65][CH3:66])[CH:55]=[CH:56]5)=[C:51]4[N:47]([CH3:46])[S:48]3(=[O:70])=[O:69])[C@H:15]([CH3:16])[C@H:11]12)[CH3:9])=[O:6])[CH:2]=[CH2:3]
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Komponenten

7

Edukt 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 11046746allyl (1S,5R,6S)-2-(hydroxymethyl)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methylcarbapen-2-em-3-carboxylateHCID 155380561-Methyl-8-triethylsilanyloxymethyl-1,3-dihydro-2-thia-1,3-diaza-cyclopenta[alpha]naphthalene 2,2-dioxide

Produkt 1

HCID 15538057
allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methyl-2-(1-methyl-2,2-dioxo-8-triethylsilanyloxymethyl-1,2-dihydro-2-thia-1,3-diaza-cyclopenta[alpha]naphthalen-3-ylmethyl)-carbapen-2-em-3-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6212ChloroformLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

A solution of allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-2-hydroxymethyl-1-methyl-carbapen-2-em-3-carboxylate (365 mg, 1.0 mmol), triphenylphosphine (315 mg, 1.2 mmol), and 1-methyl-8-triethylsilanyloxymethyl-1,3-dihydro-2-thia-1,3-diaza-cyclopenta[α]naphthalene 2,2-dioxide (416 mg, 1.1 mmol) in anhydrous tetrahydrofuran (7 mL) is cooled in an ice-bath and stirred under a nitrogen atmosphere while diisopropyl azodicarboxylate (0.24 mL, 1.2 mmol) is added dropwise over a few minutes. The resulting solution is stirred in the cold for 30 minutes, then diluted with chloroform, washed with 5% aqueous sodium bicarbonate and brine, dried over sodium sulfate, filtered and evaporated under vacuum. The residue is purified by silica gel flash chromatography, eluting with hexane-ethyl acetate, to afford allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methyl-2-(1-methyl-2,2-dioxo-8-triethylsilanyloxymethyl-1,2-dihydro-2-thia-1,3-diaza-cyclopenta[α]naphthalen-3-ylmethyl)-carbapen-2-em-3-carboxylate.

Aufarbeitung

  1. additionis added dropwise over a few minutes
  2. washwashed with 5% aqueous sodium bicarbonate and brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated under vacuum
  6. customThe residue is purified by silica gel flash chromatography
  7. washeluting with hexane-ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-ff41e205f0f3407dacd8d82812068230
Quelldatensatz
uspto-grants-2001_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06291448B1

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