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

HRID 1708101ノート

反応式

HRID 1708101 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].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

参加物

6

反応物 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

生成物 1

HCID 10373430(E)-9-[2-(t-butyldiphenylsilyloxy)methyl-4(diisopropoxyphosphoryl)but-3-enyloxy]-2-[di-(t-butoxycarbonyl)]amino-6-methoxypurine収率 67.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

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%).

後処理

  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)

出典と根拠

ORDレコード
ord-d390db5677be406a8aca84902b8c3ee1
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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