Trimethylsilyl triflate → HCID 118005613、化合物

HRID 1488247ノート

反応式

HRID 1488247 の反応式
[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

参加物

5

反応物 3

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

生成物 1

HCID 118005613HCID 118005613、化合物

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-98d27abb5c4d4818b61c2eea274bbcce
出典データセット
uspto-grants-2016_08
特許番号
US09427475B2

反応ノート

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