Triphenylphosphine → (E)-9-[2-(t-butyldiphenylsilyloxy)methyl-4(diisopropoxyphosphoryl)but-3-enyloxy]-2-[di-(t-butoxycarbonyl)]amino-6-methoxypurine

HRID 1708101Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1708101
[C:1]([O:5][C:6]([N:8]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[C:9]1[N:17]=[C:16]2[C:12]([N:13]=[CH:14][N:15]2[OH:18])=[C:11]([O:19][CH3:20])[N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Si:47]([O:64][CH2:65][CH:66]([CH2:79]O)/[CH:67]=[CH:68]/[P:69](=[O:78])([O:74][CH:75]([CH3:77])[CH3:76])[O:70][CH:71]([CH3:73])[CH3:72])([C:60]([CH3:63])([CH3:62])[CH3:61])([C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1)[C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[Si:47]([O:64][CH2:65][CH:66](/[CH:67]=[CH:68]/[P:69]([O:74][CH:75]([CH3:77])[CH3:76])([O:70][CH:71]([CH3:72])[CH3:73])=[O:78])[CH2:79][O:18][N:15]1[CH:14]=[N:13][C:12]2[C:16]1=[N:17][C:9]([N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])=[N:10][C:11]=2[O:19][CH3:20])([C:60]([CH3:63])([CH3:62])[CH3:61])([C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1)[C:48]1[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=1

Komponenten

6

Edukt 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 10436173diisopropyl (E)-3-(t-butyldiphenylsilyloxy)methyl-4-hydroxybut-1-enylphosphonateHCID 145239662-[Bis-(t-butoxycarbonyl)amino]-9-hydroxy-6-methoxypurine

Produkt 1

HCID 10373430(E)-9-[2-(t-butyldiphenylsilyloxy)methyl-4(diisopropoxyphosphoryl)but-3-enyloxy]-2-[di-(t-butoxycarbonyl)]amino-6-methoxypurineAusbeute 67,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

A mixture of 2-[di-(t-butoxycarbonyl)]amino-9-hydroxy-6-methoxypurine (0.62 g, 1.6 mmol), triphenylphosphine (0.43 g, 1.6 mmol), and diisopropyl (E)-3-(t-butyldiphenylsilyloxy)methyl-4-hydroxybut-1-enylphosphonate (0.6 g, 1.2 mmol) in anhydrous THF (15 ml) at 0° C. was treated dropwise, slowly, with diethyl azodicarboxylate (0.25 g, 1.6 mmol). After stirring overnight at room temperature, the solvent was removed in vacuo and the residue chromatographed on silica gel, eluting with acetone-hexane (1:2) to give (E)-9-[2-(t-butyldiphenylsilyloxy)methyl-4(diisopropoxyphosphoryl)but-3-enyloxy]-2-[di-(t-butoxycarbonyl)]amino-6-methoxypurine as a gum (0.7 g, 66%); υmax (KBr) 2977, 2932, 2858, 1792, 1757, 1734, 1592, 1472, and 1427 cm-1 ; δH (CDCl3) 1.06 [9H, s, C(CH3)3 ], 1.30 [12H, s, 2×CH(CH3)2 ], 1.43 (18H, s, 2×C(CH3) 3 ], 2.92 (1H, CH), 3.85 (2H, m, CH2), 4.15 (3H, s, OCH3), 4.4-4.75 [4H, CH2, 2×CH (CH3)2 ], 5.91 (1H, ddd, J 1, 17 and 19 Hz, PCH=CH), 6.77 (1H, ddd, J 8, 17 and 25Hz, PCH=H) , 7.3-7.85 (11H, m, 2×C6H5, H-8) (Found: C, 59.77; H, 7.52;N, 7.79%. C43H62N5O10PSi requires C, 59.50; H, 7.20; N, 8.07%).

Aufarbeitung

  1. additionwas treated dropwise
  2. customthe solvent was removed in vacuo
  3. customthe residue chromatographed on silica gel
  4. washeluting with acetone-hexane (1:2)

Quellen und Nachweise

ORD-Eintrag
ord-d390db5677be406a8aca84902b8c3ee1
Quelldatensatz
uspto-grants-1994_10
Patentnummer
US05356886

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