Trimethylsilyl triflate → HCID 118005613, 화합물

HRID 1488247노트

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HRID 1488247 반응식
[C:1]([O:9][C@H:10]1[C@@H:21]([O:22][C:23](=[O:30])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@H:20]([O:31][C:32](=[O:39])[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@@H:19]([CH2:40][OH:41])[O:18][C@@H:11]1[O:12][CH2:13][CH2:14][N:15]=[N+:16]=[N-:17])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:42]([O:50][C@H:51]1[C@@H:63]([O:64][C:65](=[O:72])[C:66]2[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=2)[C@H:62]([O:73][C:74](=[O:81])[C:75]2[CH:80]=[CH:79][CH:78]=[CH:77][CH:76]=2)[C@@H:61]([CH2:82][O:83][C:84](=[O:91])[C:85]2[CH:90]=[CH:89][CH:88]=[CH:87][CH:86]=2)[O:60][C@@H:52]1OC(=N)C(Cl)(Cl)Cl)(=[O:49])[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>C(Cl)Cl>[C:1]([O:9][C@H:10]1[C@@H:21]([O:22][C:23](=[O:30])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@H:20]([O:31][C:32](=[O:39])[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@@H:19]([CH2:40][O:41][C@H:52]2[O:60][C@H:61]([CH2:82][O:83][C:84](=[O:91])[C:85]3[CH:90]=[CH:89][CH:88]=[CH:87][CH:86]=3)[C@@H:62]([O:73][C:74](=[O:81])[C:75]3[CH:76]=[CH:77][CH:78]=[CH:79][CH:80]=3)[C@H:63]([O:64][C:65](=[O:72])[C:66]3[CH:67]=[CH:68][CH:69]=[CH:70][CH:71]=3)[C@@H:51]2[O:50][C:42](=[O:49])[C:43]2[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=2)[O:18][C@@H:11]1[O:12][CH2:13][CH2:14][N:15]=[N+:16]=[N-:17])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

참가 물질

5

반응물 3

HCID 65367Trimethylsilyl triflateHCID 10963703alpha-D-Mannopyranose, 2,3,4,6-tetrabenzoate 1-(2,2,2-trichloroethanimidate)HCID 117996071HCID 117996071, 화합물

생성물 1

HCID 118005613HCID 118005613, 화합물

시약·촉매·용매 1

HCID 6344Dichloromethane용매

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온도
-78 °C

실험 절차

In a 100 mL round bottom flask was added 2-azidoethyl 2,3,4-tri-O-benzoyl-α-D-mannopyranoside (720 mg, 1.282 mmol), 2,3,4,6-tetra-O-benzoyl-1-O-(2,2,2-trichloroethanimidoyl)-α-D-mannopyranose (1.14 g, 1.539 mmol) and 4 Å molecular sieves (300 mg). To the above mixture was added CH2Cl2 (10 mL). The reaction mixture was cooled to -78° C. To the above mixture was added TMSOTf (23.2 μL, 0.128 mmol). The mixture was allowed to gradually warm to 0° C. and stirred for 30 min. The reaction was then quenched with sat. NaHCO3, and the mixture was filtered through a pad of Celite. The filtrate was diluted with CH2Cl2 (20 mL), washed with brine and water. The organic phase was dried over MgSO4, filtered and concentrated. The residue was purified by flash chromatography on silica gel (80 g), eluting with 0-100% EtOAc in hexanes, to give the title product. LC-MS Method A: m/e=1157.64 [M+18] and 1163.52 [M+Na]; Rt=3.01 min. 1H NMR (CDCl3) δ 7.2-8.3 (m, 25H), 6.0 (t, 1H), 5.8 (t, 1H), 5.7 (m, 2H), 5.4 (s, 1H), 5.38 (m, 1H), 5.2 (s, 1H), 4.7 (dd, 1H), 4.6 (dd, 1H), 4.45 (m, 1H), 4.35 (dd, 1H), 3.9-4.0 (m, 2H), 3.8 (m, 2H), 3.7 (m, 1H), 3.4 (m, 2H).

후처리

  1. temperatureto gradually warm to 0° C.
  2. customThe reaction was then quenched with sat. NaHCO3
  3. filtrationthe mixture was filtered through a pad of Celite
  4. additionThe filtrate was diluted with CH2Cl2 (20 mL)
  5. washwashed with brine and water
  6. dry with materialThe organic phase was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography on silica gel (80 g)
  10. washeluting with 0-100% EtOAc in hexanes

출처 및 근거

ORD 기록
ord-98d27abb5c4d4818b61c2eea274bbcce
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09427475B2

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