Trimethylsilyl triflate → HCID 118005649, compound

HRID 1488242Notes

Reaction equation

HRID 1488242 reaction equation
[C:1]([O:9][C@H:10]1[C@@H:21]([OH:22])[C@H:20]([O:23][C:24](=[O:31])[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@H:19]([CH2:32][O:33][C:34]([C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=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.[C:53]([O:61][C@H:62]1[C@@H:74]([O:75][C:76](=[O:83])[C:77]2[CH:82]=[CH:81][CH:80]=[CH:79][CH:78]=2)[C@H:73]([O:84][C:85](=[O:92])[C:86]2[CH:91]=[CH:90][CH:89]=[CH:88][CH:87]=2)[C@@H:72]([CH2:93][O:94][C:95](=[O:102])[C:96]2[CH:101]=[CH:100][CH:99]=[CH:98][CH:97]=2)[O:71][C@@H:63]1OC(=N)C(Cl)(Cl)Cl)(=[O:60])[C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=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@H:63]2[O:71][C@H:72]([CH2:93][O:94][C:95](=[O:102])[C:96]3[CH:101]=[CH:100][CH:99]=[CH:98][CH:97]=3)[C@@H:73]([O:84][C:85](=[O:92])[C:86]3[CH:87]=[CH:88][CH:89]=[CH:90][CH:91]=3)[C@H:74]([O:75][C:76](=[O:83])[C:77]3[CH:78]=[CH:79][CH:80]=[CH:81][CH:82]=3)[C@@H:62]2[O:61][C:53](=[O:60])[C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=2)[C@H:20]([O:23][C:24](=[O:31])[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@H:19]([CH2:32][O:33][C:34]([C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)([C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[C:47]2[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=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:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 10963703alpha-D-Mannopyranose, 2,3,4,6-tetrabenzoate 1-(2,2,2-trichloroethanimidate)HCID 117996009HCID 117996009, compound

Product 1

HCID 118005649HCID 118005649, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

In a 100 mL round bottom flask was added 2-azidoethyl 2,4-bis-O-benzoyl-6-O-trityl-α-D-mannopyranoside (400 mg, 0.572 mmol), 2,3,4,6-tetra-O-benzoyl-1-O-(2,2,2-trichloroethanimidoyl)-α-D-mannopyranose (508 mg, 0.686 mmol) and 4 Å molecular sieves (300 mg). To the above mixture was added CH2Cl2 (5 mL). The reaction mixture was cooled to −78° C., to which was added TMSOTf (10.33 μL, 0.057 mmol). The mixture was allowed to gradually warm to 0° C. and stirred for 30 min. The reaction was then quenched with sat'd NaHCO3, and 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, 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=1278.80 [M+1]; Rt=3.14 min. 1H NMR (CDCl3) δ 7.1-8.3 (m, 30H), 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).

Workup

  1. temperatureto gradually warm to 0° C.
  2. customThe reaction was then quenched with sat'd NaHCO3
  3. filtrationfiltered 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. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on silica gel (80 g)
  9. washeluting with 0-100% EtOAc in hexanes

Sources & evidence

ORD record
ord-3e737a29ca014fb3b909a2967fa219bf
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

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