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Dibenzylamine → tert-Butyl (2S,3S)-3-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl-(dimethyl)silyl]oxy}-5-(3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-1(2H)-pyrimidinyl)-tetrahydro-2-furanyl]-2-(dibenzylamino)-3-hydroxy-propanoate

HRID 25678
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 25678
BrCC(OC(C)(C)C)=O.C(NCC1C=CC=CC=1)C1C=CC=CC=1.[CH2:25]([N:32]([CH2:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)[CH:33]([CH3:41])[C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C([N-]C(C)C)(C)C.[Li+].[Si:57]([O:64][C@H:65]1[C@@H:69]([O:70][Si:71]([C:74]([CH3:77])([CH3:76])[CH3:75])([CH3:73])[CH3:72])[C@H:68]([N:78]2[CH:83]=[CH:82][C:81](=[O:84])[N:80]([CH2:85][C:86]3[CH:91]=[CH:90][C:89]([O:92][CH3:93])=[CH:88][CH:87]=3)[C:79]2=[O:94])[O:67][C@H:66]1[CH:95]=[O:96])([C:60]([CH3:63])([CH3:62])[CH3:61])([CH3:59])[CH3:58]>O1CCOCC1.O1CCCC1.C(OCC)(=O)C.C(O)C>[CH2:25]([N:32]([CH2:42][C:43]1[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=1)[CH:33]([CH3:41])[C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1.[C:60]([Si:57]([CH3:59])([CH3:58])[O:64][C@H:65]1[C@@H:69]([O:70][Si:71]([C:74]([CH3:75])([CH3:77])[CH3:76])([CH3:72])[CH3:73])[C@H:68]([N:78]2[CH:83]=[CH:82][C:81](=[O:84])[N:80]([CH2:85][C:86]3[CH:87]=[CH:88][C:89]([O:92][CH3:93])=[CH:90][CH:91]=3)[C:79]2=[O:94])[O:67][C@@H:66]1[C@@H:95]([OH:96])[C@H:33]([N:32]([CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)[CH2:42][C:43]1[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=1)[C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])([CH3:61])([CH3:62])[CH3:63]
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Komponenten

11

Edukt 5

HCID 7656DibenzylamineHCID 79177tert-Butyl bromoacetateHCID 2724682Lithium diisopropylamideHCID 14557753tert-Butyl 2-(dibenzylamino)-propanoateHCID 86587931(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-[3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl]-tetrahydro-furan-2-carbaldehyde

Produkt 2

HCID 14557753tert-Butyl 2-(dibenzylamino)-propanoate
HCID 59065932tert-Butyl (2S,3S)-3-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl-(dimethyl)silyl]oxy}-5-(3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-1(2H)-pyrimidinyl)-tetrahydro-2-furanyl]-2-(dibenzylamino)-3-hydroxy-propanoateAusbeute 14,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 702EthanolLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

tert-Butyl 2-(dibenzylamino)-propanoate was prepared from tert-butyl bromoacetate (10 ml, 68 mmole) and dibenzylamine (26.5 ml, 138 mmole) in 1,4-dioxane (20 ml) and abs. ethanol (25 ml), following the literature procedure (Scolastico, C. Tetrahedron Letts., 1987, 43, 2317). A solution of tert-butyl 2-(dibenzylamino)-propanoate (4.75 g, 15.23 mmole) in anhydrous tetrahydrofuran (60 ml) was cooled at −78° C. under argon. A solution of lithium diisopropylamide (7.6 ml, 15.23 mmole, 2.0 M solution in tetrahydrofuran, Aldrich) was introduced to this cooled solution over a period of 15 min, and the resulting reddish orange solution was stirred at this temperature for 1 h. A solution of 1-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-[3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl]-tetrahydro-furan-2-carbaldehyde (4.5 g, 7.62 mmole, obtained from Reference Example 3) in anhydrous tetrahydrofuran was added via syringe to the cooled mixture over a period of 15 min. The resulting mixture was stirred at −30° C. for 15 h under argon, and diluted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated to dryness in vacuo. The residue was chromatographed (flash column, silica gel, methylene chloride:n-hexane:methanol:diethyl ether=49:49:1:1) to give tert-butyl (2S,3S)-3-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl-(dimethyl)silyl]oxy}-5-(3-(4-methoxybenzyl)-2,4-dioxo-3,4-dihydro-1(2H)-pyrimidinyl)-tetrahydro-2-furanyl]-2-(dibenzylamino)-3-hydroxypropanoate (990 mg, 14.4%) as a white amorphous solid.

Aufarbeitung

  1. stirringThe resulting mixture was stirred at −30° C. for 15 h under argon
  2. washThe organic layer was washed with saturated sodium bicarbonate aqueous solution and saturated sodium chloride solution
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated to dryness in vacuo
  6. customThe residue was chromatographed (flash column, silica gel, methylene chloride:n-hexane:methanol:diethyl ether=49:49:1:1)

Quellen und Nachweise

ORD-Eintrag
ord-666ec7b0d6cb4e00a7d79c307aeb5fad
Quelldatensatz
uspto-grants-2005_02
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06858591B2

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