Triphenylphosphine → HCID 90410666, 화합물

HRID 1754595노트

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HRID 1754595 반응식
[CH2:1]([O:8][CH2:9][C@H:10]([C@H:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH3:14])[CH2:11]O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:23]([N:31]1[C:36](=[O:37])[C:35]([CH3:38])=[CH:34][NH:33][C:32]1=[O:39])(=[O:30])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[CH2:1]([O:8][CH2:9][C@@H:10]([CH2:11][N:33]1[CH:34]=[C:35]([CH3:38])[C:36](=[O:37])[N:31]([C:23](=[O:30])[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:32]1=[O:39])[C@H:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH3:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

참가 물질

6

반응물 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 10933275N3-benzoylthymineHCID 11067317(2R,3R)-2-((benzyloxy)methyl)-3-(tert-butyldimethylsiloxy)butan-1-ol

생성물 1

HCID 90410666HCID 90410666, 화합물수율 81%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To a cold (ice/water bath) solution of (2R,3R)-2-((benzyloxy)methyl)-3-(tert-butyldimethylsiloxy)butan-1-ol (4) (W.-H. Ham et al. J. Org. Chem. 2000, 65, 8372-8374) 1.5 g, 4.6 mmol), 3-benzoylthymine (1.5 g, 6.5 mmol) and triphenylphosphine (1.71 g, 6.5 mmol) in 50 ml of anhydrous THF was added dropwise via syringe with stirring (1.26 ml, 6.5 mmol) of diisopropylazodicarboxylate. The reaction was removed from the bath and stirred at room temperature for 2 hrs and then concentrated. The reaction was diluted with ether (50 ml) and hexane (50 ml) to precipitate some of triphenylphosphine oxide and the DIPADC by-product. The solids were filtered off and the filtrate concentrated. The resultant crude product, which still contained some Ph3PO, was chromatographed on silica eluting with 20% ethyl acetate in hexane. Concentration of the pure product fractions afforded 2.0 g (81%) of 5 as a colorless viscous srup. 1H NMR (CDCl3): δ 7.85 (d, J=8.4 Hz, 2H), 7.58 (t, J=7.5 Hz, 1H), 7.42 (t, J=7.8 Hz, 2H), 7.35-7.25 (m, 5H), 7.06 (d, J=1.2 Hz, 1H), 4.42 (s, 2H), 3.98 (m, 2H), 3.61 (m, 1H), 3.46 (d, J=5.7 Hz, 2H), 2.08 (m, 1H), 1.83 (s, 3H), 1.16 (d, J=6.6 Hz, 3H), 0.84 (s, 9H), 0.02 (s, 3H), 0.00 (s, 3H).

후처리

  1. customThe reaction was removed from the bath
  2. concentrationconcentrated
  3. additionThe reaction was diluted with ether (50 ml) and hexane (50 ml)
  4. customto precipitate some of triphenylphosphine oxide
  5. filtrationThe solids were filtered off
  6. concentrationthe filtrate concentrated
  7. customwas chromatographed on silica eluting with 20% ethyl acetate in hexane

출처 및 근거

ORD 기록
ord-6367e2a10f124a00bf0b6ba058e24a95
출처 데이터셋
uspto-grants-2015_10
특허 번호
US09169256B2

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