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

HRID 1708101노트

반응식

HRID 1708101 반응식
[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

참가 물질

6

반응물 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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

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%).

후처리

  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)

출처 및 근거

ORD 기록
ord-d390db5677be406a8aca84902b8c3ee1
출처 데이터셋
uspto-grants-1994_10
특허 번호
US05356886

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