HCID 10622632, compound → HCID 10527471, compound

HRID 1016267Notes

Reaction equation

HRID 1016267 reaction equation
[C:1]([O:4][C@H:5]1[C@H:10]([CH:11]=[O:12])[CH2:9][C@H:8]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:6]12[CH3:7])[C:21]1[CH:20]=[CH:19][C:18]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[CH:17][C:16]=1[CH2:15][CH2:14]3)(=[O:3])[CH3:2].CC(C)=[O:35].OS(O)(=O)=O.O=[Cr](=O)=O>CC(C)=O.CO.O>[CH2:26]([O:25][C:18]1[CH:19]=[CH:20][C:21]2[C@@H:22]3[C@H:13]([C@H:8]4[C@@:6]([CH2:24][CH2:23]3)([CH3:7])[C@@H:5]([O:4][C:1](=[O:3])[CH3:2])[C@H:10]([C:11]([OH:35])=[O:12])[CH2:9]4)[CH2:14][CH2:15][C:16]=2[CH:17]=1)[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

6

Reactant 2

HCID 10622632HCID 10622632, compoundHCID 131709961Jones' reagent

Product 1

HCID 10527471HCID 10527471, compoundYield 92%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 824 mg (1.90 mmol) of 5 in 120 mL of acetone was cooled to 0° C. and 710 μL of Jones reagent solution (8 M solution of CrO3 in aqueous H2SO4)37 was added. The reaction mixture was stirred at 0° C. for 30 min, diluted with MeOH (20 mL) and H2O (20 mL), concentrated to about 30 mL, and extracted with CH2Cl2 (3×, 70 mL). Combined organic extracts were dried over Na2SO4 and concentrated in vacuo. Purification of the residue by flash chromatography on a 2×17 cm column of silica gel using EtOH/CH2Cl2 (5:95) gave 784.4 mg (92%) of 6 as a white foam. Data for 6: TLC, T-4, Rf0.78. 1H NMR (500 MHz, CDCl3) δ 0.87 (s, 3H, H-18), 2.10 (s, 3H, OAc), 5.02 (d, 1H, J=7.1 Hz, H-17α), 5.04(s, 2H, benzylic), 6.72 (d, 1H, J=2.8 Hz, H-4), 6.79 (dd, 1H, J=8.5, 2.8 Hz, H-2), 7.20 (d, 1H, J=8.5 Hz, H-1), 7.31-7.44 (m, 5H, Ar—H); HRMS (ES) calcd for C28H32O5Na (M+Na+) m/e 471.2147, found m/e 471.2146.

Workup

  1. concentrationconcentrated to about 30 mL
  2. extractionextracted with CH2Cl2 (3×, 70 mL)
  3. dry with materialCombined organic extracts were dried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customPurification of the residue by flash chromatography on a 2×17 cm column of silica gel

Sources & evidence

ORD record
ord-0c22322a15b74b8ca81f3b75d384e656
Source dataset
uspto-grants-2002_11
Patent number
US06476012B2

Reaction notes

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