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

HRID 1708088ノート

反応式

HRID 1708088 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-868a4e242cb3493fb209a3d197dca8c7
出典データセット
uspto-grants-1994_10
特許番号
US05356886

反応ノート

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