Hexamethylphosphoramide → HCID 11991896, compound

HRID 2386187Notes

Reaction equation

HRID 2386187 reaction equation
[Si](OC(C1OC(I)=CN=1)CCCCCCC1C=CC=CC=1)(C(C)(C)C)(C)C.[Si]([O:35][CH:36]([C:49]1[O:50][C:51]([C:54]([F:57])([F:56])[F:55])=[CH:52][N:53]=1)[CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)(C(C)(C)C)(C)C.CN(P(N(C)C)(N(C)C)=O)C.FS(C(C(OC)=O)(F)F)(=O)=O.[NH4+].[Cl-]>CN(C=O)C.[Cu]I>[C:43]1([CH2:42][CH2:41][CH2:40][CH2:39][CH2:38][CH2:37][C:36]([C:49]2[O:50][C:51]([C:54]([F:57])([F:56])[F:55])=[CH:52][N:53]=2)=[O:35])[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1

Participants

7

Reactant 4

HCID 12679HexamethylphosphoramideHCID 25517Ammonium ChlorideHCID 547667Methyl 2,2-difluoro-2-(fluorosulfonyl)acetateHCID 86640153HCID 86640153, compound

Product 1

HCID 11991896HCID 11991896, compoundYield 76.8%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

2-(1-(tert-Butyldimethylsilyloxy)-7-phenylheptyl)-5-(trifluoromethyl)oxazole 2-(1-(tert-Butyldimethylsilyloxy)-7-phenylheptyl)-5-iodooxazole (24 mg, 0.048 mmol), HMPA (5 equiv), CuI (1.2 equiv) and FSO2CF2CO2CH3 (5 equiv) were dissolved in DMF (1 mL) and heated to 70° C. in a sealed vial for 5 h. The mixture was cooled to room temperature, saturated aqueous NH4Cl was added and the aqueous layer was extracted with ether. The ether layer was washed with saturated aqueous NaHCO3, washed with saturated aqueous NaCl and dried over sodium sulfate. Flash chromatography (0-2% EtOAc/hexanes) yielded the title compound as a light yellow oil (12 mg, 55%): 1H NMR (CDCl3, 600 MHz) δ 7.38 (s, 1H), 7.28-7.25 (m, 2H), 7.18-7.15 (m, 3H), 4.81 (t, 1H, J=6.0 Hz), 2.59 (t, 2H, J=7.8 Hz), 1.90-1.82 (m, 2H), 1.61-1.59 (m, 2H), 1.43-1.33 (m, 6H), 0.87 (s, 9H), 0.07 (s, 3H), −0.04 (s, 3H); 13C NMR (CDCl3, 150 MHz) δ 168.5, 143.6, 140.5 (d, J=45 Hz), 129.2, 129.1, 128.8 (d, J=2.7 Hz), 126.5, 119.7 (d, J=265 Hz), 69.3, 37.0, 36.8, 32.2, 29.9, 26.5, 26.5, 25.8, 19.0, −4.4, −4.4.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. extractionthe aqueous layer was extracted with ether
  3. washThe ether layer was washed with saturated aqueous NaHCO3
  4. washwashed with saturated aqueous NaCl
  5. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-6cf042233f7e4b639c8613cb90663698
Source dataset
uspto-grants-2012_09
Patent number
US08268817B2

Reaction notes

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