Chloroform → HCID 67432486, compound

HRID 1842842Notes

Reaction equation

HRID 1842842 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:31](O)[C@@H:12]2[O:13][Si:14]([CH:28]([CH3:30])[CH3:29])([CH:25]([CH3:27])[CH3:26])[O:15][Si:16]([CH:22]([CH3:24])[CH3:23])([CH:19]([CH3:21])[CH3:20])[O:17][CH2:18][C@H:11]2[C:10]1=[CH2:33])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(S(F)(F)[F:40])CC)C.C(Cl)(Cl)Cl>C(Cl)Cl>[CH2:1]([O:8][C@@H:9]1[C@@H:31]([F:40])[C@@H:12]2[O:13][Si:14]([CH:28]([CH3:30])[CH3:29])([CH:25]([CH3:27])[CH3:26])[O:15][Si:16]([CH:22]([CH3:24])[CH3:23])([CH:19]([CH3:21])[CH3:20])[O:17][CH2:18][C@H:11]2[C:10]1=[CH2:33])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6212ChloroformHCID 123472(Diethylamino)sulfur trifluorideHCID 67433790HCID 67433790, compound

Product 1

HCID 67432486HCID 67432486, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of alcohol 6 (6.5 g, 13.2 mmol) in anhydrous CH2Cl2, (diethylamino)sulfur trifluoride (DAST, 1.84 mL, 13.9 mmol) was added slowly at room temperature. The reaction mixture was quenched with iced H2O after 20 min. The organic layer was collected and the aqueous phase was extracted with dichloromethane. The organic layer was then combined, dried over magnesium sulfate, filtered and concentrated in vacuo. The crude residue was used immediately for the next deprotection step. The analytic sample of 8 was obtained by the purification using column chromatography on a silica gel (EtOAc:Hexanes=1:100 to 1:20).[α]24D −104.08° (c 0.51, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.39-7.26 (m, 5H), 5.36 (t, J=2.5 Hz, 1H), 5.20 (dd, J=2.5 and 5.0 Hz, 1H), 4.92 (ddd, J=6.0, 7.5 and 55.0 Hz, 1H), 4.78 (d, J=11.5 Hz, 1H), 4.65 (d, J=11.5 Hz, 1H), 4.31-4.26 (m, 1H), 4.23-4.16 (m, 1H), 4.01-3.92 (m, 1H), 1.08-0.94 (m, 27H); 13C NMR (100 MHz, CDCl3) δ 142.6 (d, J=9.2 Hz), 137.9, 128.4, 127.8, 127.7, 112.7, 103.4 (d, J=189.0 Hz), 80.4 (d, J=21.3 Hz), 73.8 (d, J=19.8 Hz), 71.3, 61.6, 48.8 (d, J=5.3 Hz), 17.5, 17.4, 17.1, 17.0, 16.9, 16.8, 13.4, 13.3, 12.7, 12.5. HR-MS Calcd. for (C26H43FO4Si2+H)+ 495.2762, found 495.2769.

Workup

  1. customThe reaction mixture was quenched with iced H2O after 20 min
  2. customThe organic layer was collected
  3. extractionthe aqueous phase was extracted with dichloromethane
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe analytic sample of 8 was obtained by the purification

Sources & evidence

ORD record
ord-2a7f75697f134ef490683e4e670f8602
Source dataset
uspto-grants-2015_02
Patent number
US08946244B2

Reaction notes

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