Triphenylphosphine → HCID 10373430, compound

HRID 1708101Notes

Reaction equation

HRID 1708101 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].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

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 10436173HCID 10436173, compoundHCID 145239662-[Bis-(t-butoxycarbonyl)amino]-9-hydroxy-6-methoxypurine

Product 1

HCID 10373430HCID 10373430, compoundYield 67.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

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%).

Workup

  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)

Sources & evidence

ORD record
ord-d390db5677be406a8aca84902b8c3ee1
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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