m-Chloroperbenzoic acid → t-Butyldimethylsilyl 3-O-allyloxycarbonyl-2-azido-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3-yl)-beta-D-glucopyranoside

HRID 1045235노트

반응식

HRID 1045235 반응식
[CH2:1]([O:4][C:5]([O:7][C@H:8]1[C@H:21]([OH:22])[C@@H:20]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:19][C@@H:10]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[C@@H:9]1[N:32]=[N+:33]=[N-:34])=[O:6])[CH:2]=[CH2:3].N1C=NN=N1.C(N(CC)[P:43]1[O:49][CH2:48][C:47]2[CH:50]=[CH:51][CH:52]=[CH:53][C:46]=2[CH2:45][O:44]1)C.C1C=C(Cl)C=C(C(OO)=[O:64])C=1>C(Cl)Cl>[CH2:1]([O:4][C:5]([O:7][C@H:8]1[C@H:21]([O:22][P:43]2(=[O:64])[O:44][CH2:45][C:46]3[CH:53]=[CH:52][CH:51]=[CH:50][C:47]=3[CH2:48][O:49]2)[C@@H:20]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:19][C@@H:10]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])[CH3:14])[C@@H:9]1[N:32]=[N+:33]=[N-:34])=[O:6])[CH:2]=[CH2:3]

참가 물질

6

반응물 4

HCID 70297m-Chloroperbenzoic acidHCID 41968792,4,3-Benzodioxaphosphepin-3-amine, N,N-diethyl-1,5-dihydro-HCID 16216114t-Butyldimethylsilyl 3-O-allyloxycarbonyl-2-azido-6-O-benzyl-2-deoxy-beta-D-glucopyranosideHCID 178418441HCID 178418441, 화합물

생성물 1

HCID 16216115t-Butyldimethylsilyl 3-O-allyloxycarbonyl-2-azido-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3-yl)-beta-D-glucopyranoside수율 89%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a solution of compound 9 (1.30 g, 2.50 mmol) and 1H-tetrazole (3% wt, 10.0 mmol) in DCM (30 mL) was added N,N-diethyl-1,5-dihydro-3H-2,4,3-benzodioxaphosphepin-3-amine (1.20 g, 1.05 mmol). After the reaction mixture was stirred at room temperature for 15 min, it was cooled (−20° C.), stirred for another 10 min and then mCPBA (3.40 g, 50-55% wt, 10.0 mmol) was added. The reaction mixture was stirred at −20° C. for 20 min, and then quenched by the addition of saturated aqueous NaHCO3 (40 mL) and diluted with DCM (30 mL). The organic phase was washed with saturated aqueous NaHCO3 (2×60 mL) and brine (2×40 mL), dried (MgSO4) and filtered. Next, the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5/1-3/1, v/v) to give 10 as a pale yellow oil (1.48 g, 89%). Rf=0.40 (hexane/ethyl acetate, 1/1, v/v). [α]25D=−10.3° (c=1.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.35-7.15 (m, 9H, aromatic), 5.98-5.85 (m, 1H, OCH2CH═CH2), 5.65 (d, 1H, J=1.2 Hz, J=17.4 Hz, OCH2CH═CH2), 5.50 (d, 1H, J=1.2 Hz, J=10.5 Hz, OCH2CH═CH2), 5.18-5.01 (m, 4H, C6H4(CH2O)P), 3.81 (dd, 1H, J2,3=10.5 Hz, J3,4=9.3 Hz, H-3), 4.64-4.52 (m, 6H, H-1, H-4, OCH2CH═CH2, CH2Ph), 3.82 (d, 1H, J6a,6b=9.0 Hz, H-6a), 3.72-3.61 (m, 2H, H-5, H-6b), 3.41 (dd, 1H, J1,2=7.4 Hz, J2,3=10.5 Hz, H-2), 0.92 (s, 9H, SiC(CH3)3), 0.16 (s, 3H, Si(CH3)), 0.15 (s, 3H, Si(CH3)). 13C NMR (75 MHz, CDCl3): δ 154.38 (C═O), 138.02-127.56 (aromatic), 131.33 (OCH2CH═CH2), 118.99 (OCH2CH═CH2), 97.13 (C-1), 76.77 (C-3), 74.27 (C-4), 74.08 (C-5), 73.50 (CH2Ph), 69.06 (OCH2CH═CH2), 68.74 (C-6), 68.55 (OC6H4(CH2O)P), 68.50 (OC6H4(CH2O)P), 65.97 (C-2), 25.53 (SiC(CH3)3), 17.92 (SiC(CH3)3), −4:35 (Si(CH3)2), −5.28 (Si(CH3)2). HR MS (m/z) calculated for C31H42N3O10PSi[M+Na]+, 698.2275; found, 698.2315.

후처리

  1. temperatureit was cooled (−20° C.)
  2. stirringstirred for another 10 min
  3. stirringThe reaction mixture was stirred at −20° C. for 20 min
  4. customquenched by the addition of saturated aqueous NaHCO3 (40 mL)
  5. additiondiluted with DCM (30 mL)
  6. washThe organic phase was washed with saturated aqueous NaHCO3 (2×60 mL) and brine (2×40 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationNext, the filtrate was concentrated in vacuo
  10. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5/1-3/1

출처 및 근거

ORD 기록
ord-dfbe86cc88324aa881d814b730937920
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08563523B2

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