4-Toluenesulfonyl chloride → HCID 91462899, compound

HRID 636266Notes

Reaction equation

HRID 636266 reaction equation
[Si:1]([O:18][C@@H:19]1[C@H:24]([CH3:25])[C@H:23]([OH:26])[CH2:22][C@H:21]([C:27]([O:29][CH3:30])=[O:28])[CH2:20]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:31]1([CH3:41])[CH:36]=[CH:35][C:34]([S:37](Cl)(=[O:39])=[O:38])=[CH:33][CH:32]=1.CCN(CC)CC>CN(C1C=CN=CC=1)C.C(Cl)Cl>[Si:1]([O:18][C@@H:19]1[C@@H:24]([CH3:25])[C@H:23]([O:26][S:37]([C:34]2[CH:35]=[CH:36][C:31]([CH3:41])=[CH:32][CH:33]=2)(=[O:39])=[O:38])[CH2:22][C@@H:21]([C:27]([O:29][CH3:30])=[O:28])[CH2:20]1)([C:14]([CH3:17])([CH3:15])[CH3:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chloride3×HCID 8471Triethylamine3×HCID 11697580HCID 11697580, compound

Product 1

HCID 91462899HCID 91462899, compound

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalyst3×HCID 6344DichloromethaneSolvent2×

Procedure

To a mixture of 2.2.c (R=Me, P=TBDMS, A=COOCH3) (279 mg, 0.828 mmol), p-toluenesulfonyl chloride (323 mg, 1.69 mmol, 98%), DMAP (5.1 mg, 0.042 mmol) in 10 ml of dry CH2Cl2 at 0° C. (ice bath) was added Et3N (308 μL, 2.54 mmol). The mixture was refluxed for three days; then p-toluenesulfonyl chloride (320 mg, 1.69 mmol, 98%), DMAP (5.1 mg, 0.042 mmol) and Et3N (500 μL) were added. The resulting solution was refluxed for two days, p-toluenesulfonyl chloride (320 mg, 1.69 mmol, 98%), DMAP (5.1 mg, 0.042 mmol) and Et3N (500 μL) were added again and reflux was continued for another day. The resulting mixture was diluted with 20 ml of CH2Cl2, washed with brine and the aqueous phase was extracted with EtOAc (4×50 ml). The combined organic phases were dried over MgSO4. Filtration of the solvent, concentration and flash chromatography on silica (isooctane/EtOAc: 9:1), afforded 2.3.c (R=Me, P=TBDPS, L=OTos, A=COOCH3) (316 mg, 83.5%) as a light yellow oil.

Workup

  1. temperatureThe mixture was refluxed for three days
  2. temperatureThe resulting solution was refluxed for two days
  3. temperaturereflux
  4. waitwas continued for another day
  5. washwashed with brine
  6. extractionthe aqueous phase was extracted with EtOAc (4×50 ml)
  7. dry with materialThe combined organic phases were dried over MgSO4
  8. filtrationFiltration of the solvent, concentration and flash chromatography on silica (isooctane/EtOAc: 9:1)

Sources & evidence

ORD record
ord-5a05269a125648269fd1b919aa354e1a
Source dataset
uspto-grants-2001_02
Patent number
US06191292B1

Reaction notes

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