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

HRID 1708088Notes

Reaction equation

HRID 1708088 reaction equation
[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].O[CH2:29][CH2:30]/[CH:31]=[CH:32]/[P:33](=[O:42])([O:38][CH:39]([CH3:41])[CH3:40])[O:34][CH:35]([CH3:37])[CH3:36].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[C:24]([O:23][C:21]([N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[C:9]1[N:17]=[C:16]2[C:12]([N:13]=[CH:14][N:15]2[O:18][CH2:29][CH2:30]/[CH:31]=[CH:32]/[P:33]([O:38][CH:39]([CH3:40])[CH3:41])([O:34][CH:35]([CH3:36])[CH3:37])=[O:42])=[C:11]([O:19][CH3:20])[N:10]=1)=[O:22])([CH3:27])([CH3:26])[CH3:25]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 10399205diisopropyl (E)-4-hydroxybut-1-enylphosphonateHCID 145239662-[Bis-(t-butoxycarbonyl)amino]-9-hydroxy-6-methoxypurine

Product 1

HCID 10348554(E)-2-[di-(t-butoxycarbonyl)]amino-9-[4-(diisopropoxyphosphoryl)but-3-enyloxy]-6-methoxypurineYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 2-[di-(t-butoxycarbonyl)]amino-9-hydroxy-6-methoxypurine (154 mg, 404 μmol), diisopropyl (E)-4-hydroxybut-1-enylphosphonate (89 mg, 404 μmol) and triphenylphosphine (159 mg, 606 μmol) in dry tetrahydrofuran (4 ml) stirred at 0° C. was added diethyl azodicarboxylate (105 mg, 606 μmol). The mixture was allowed to warm to room temperature and stirred for 2.3 hr. The solvent was removed and the residue was purified by column chromatography on silica gel eluting with ethyl acetate-methanol (20:1) to give (E)-2-[di-(t-butoxycarbonyl)]amino-9-[4-(diisopropoxyphosphoryl)but-3-enyloxy]-6-methoxypurine as a colourless gum (150 mg, 62%); λmax (EtOH) 255 (12,300)nm; υmax (KBr) 3440, 3220, 2975, 1790, 1600, 1370, 1280 and 1100 cm-1 ; δH [(CD3)2SO] 1.22 (12H, dd, J 6 Hz and 7 Hz, CH(CH3)2), 1.40 (18H, S, C(CH3)3), 2.70 (2H, m, CH2), 4.08 (3H, s, CH3O), 4.53 (4H, m, CH2O and CH(CH3)2), 5.98 (1H, dd, J 17 Hz and 19 Hz, PCH=CH), 6.25 (1H, ddt, J 6 Hz, 17 Hz and 22 Hz, PCH=CH), 8.71 (1H, s, 8-H) (Found: M+ 599.2724. C26H42N5O9P requires M+ 599.2720).

Workup

  1. temperatureto warm to room temperature
  2. stirringstirred for 2.3 hr
  3. customThe solvent was removed
  4. customthe residue was purified by column chromatography on silica gel eluting with ethyl acetate-methanol (20:1)

Sources & evidence

ORD record
ord-868a4e242cb3493fb209a3d197dca8c7
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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