(Diethylamino)sulfur trifluoride → HCID 86693882, compound

HRID 1842838Notes

Reaction equation

HRID 1842838 reaction equation
[CH2:1]([O:8][C@H:9]1[C:19]2([CH2:21][CH2:20]2)[C@H:18]2[C@@H:11]([O:12][Si:13]([CH:31]([CH3:33])[CH3:32])([CH:28]([CH3:30])[CH3:29])[O:14][Si:15]([CH:25]([CH3:27])[CH3:26])([CH:22]([CH3:24])[CH3:23])[O:16][CH2:17]2)[C@H:10]1O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(S(F)(F)[F:41])CC)C>C(Cl)Cl>[CH2:1]([O:8][C@H:9]1[C:19]2([CH2:21][CH2:20]2)[C@H:18]2[C@@H:11]([O:12][Si:13]([CH:31]([CH3:33])[CH3:32])([CH:28]([CH3:30])[CH3:29])[O:14][Si:15]([CH:25]([CH3:27])[CH3:26])([CH:22]([CH3:24])[CH3:23])[O:16][CH2:17]2)[C@@H:10]1[F:41])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 123472(Diethylamino)sulfur trifluorideHCID 86718973HCID 86718973, compound

Product 1

HCID 86693882HCID 86693882, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of alcohol 25 (5.1 g, 10.7 mmol) in anhydrous CH2Cl2, (diethylamino) sulfur trifluoride (DAST) (9.3 ml, 70.5 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 Na2SO4 and the volatiles removed under reduced pressure. The crude residue was purified by flash silica gel column chromatography (1% EtOAc/Hexane) to give 26 (2.5 g, 49%). [α]24D −98.08° (c 0.51, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.39-7.26 (m, 5H), 4.92 (ddd, J=6.0, 7.5 & 5.5 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, 2H), 2.70 (m, 1H) 1.08-0.94 (m, 28H), 0.72 (m, 1H), 0.68-0.43 (m, 2H), 0.28 (m, 1H); 13C NMR (125 MHz, CDCl3) δ142.6 (d, J=9.2 Hz), 141.8, 137.9, 128.4, 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), 29.4, 24.5, 17.5, 17.4, 17.3, 17.2, 17.1, 17.0, 16.9, 16.8, 13.4, 13.3, 12.7, 12.5, 7.9; HR-MS Calcd. For (C27H45FO4Si2+H)+ 509.2840, found 509.2923.

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 Na2SO4
  5. customthe volatiles removed under reduced pressure
  6. customThe crude residue was purified by flash silica gel column chromatography (1% EtOAc/Hexane)

Sources & evidence

ORD record
ord-68ab06c393e74b9caf2311e44013178a
Source dataset
uspto-grants-2015_02
Patent number
US08946242B2

Reaction notes

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