Phosphate → HCID 66937743, compound

HRID 1363835Notes

Reaction equation

HRID 1363835 reaction equation
[Si:1]([O:8][CH:9]1[CH2:20][C:19](=[O:21])[O:18][C@H:17](/[C:22](/[CH3:35])=[CH:23]/[CH2:24][O:25]CC2C=CC(OC)=CC=2)[C@@H:16]([CH3:36])[CH:15]=[CH:14][C@@H:13]2[O:37][C@H:38]([C:40]3[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=3)[O:39][C@:12]2([CH3:46])[CH2:11][CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].P([O-])([O-])([O-])=O.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>ClCCl>[Si:1]([O:8][CH:9]1[CH2:20][C:19](=[O:21])[O:18][C@H:17](/[C:22](/[CH3:35])=[CH:23]/[CH2:24][OH:25])[C@@H:16]([CH3:36])[CH:15]=[CH:14][C@@H:13]2[O:37][C@H:38]([C:40]3[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=3)[O:39][C@:12]2([CH3:46])[CH2:11][CH2:10]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 1061PhosphateHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinone3×HCID 66938091HCID 66938091, compound

Product 1

HCID 66937743HCID 66937743, compoundYield 79.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(2S,3aS,4E,6S,7S,13aR)-11-{[tert-butyl(dimethyl)silyl]oxy}-7-{(1E)-3-[(4-methoxybenzyl)oxy]-1-methylprop-1-en-1-yl}-6,13a-dimethyl-2-phenyl-3a,6,7,10,11,12,13,13a-octahydro-9H-[1,3]dioxolo[4,5-f]oxacyclododecin-9-one (710 mg, 1.09 mmol) was dissolved in dichloromethane (14.0 ml) and a phosphate buffer (pH=7, 1.40 ml). 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (297 mg, 1.31 mmol) was added to the reaction solution at 0° C. and stirred for three hours. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (74.3 mg, 0.33 mmol) was added and the reaction solution was stirred at 0° C. for one and a half hour. After 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (74.3 mg, 0.33 mmol) was added and the reaction solution was stirred at 0° C. for further 30 minutes, the reaction solution was filtered with silica gel (Fuji Silysia, commercial name Chromatorex, NH, 200-350 mesh). The filtrate was washed with a saturated sodium hydrogen carbonate aqueous solution, distilled water and brine sequentially and dried over anhydrous magnesium sulfate. After the drying agent was filtered off, the organic layer was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (Kanto Chemical, commercial name Silica gel 60N, granular, neutral, 0.040 mm-0.100 mm; n-heptane:ethyl acetate=4:1→3:1) to obtain the title compound (460 mg) as a colorless needle.

Workup

  1. stirringthe reaction solution was stirred at 0° C. for one and a half hour
  2. stirringthe reaction solution was stirred at 0° C. for further 30 minutes
  3. filtrationthe reaction solution was filtered with silica gel (Fuji Silysia, commercial name Chromatorex, NH, 200-350 mesh)
  4. washThe filtrate was washed with a saturated sodium hydrogen carbonate aqueous solution
  5. distillationdistilled water and brine sequentially
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationAfter the drying agent was filtered off
  8. concentrationthe organic layer was concentrated under reduced pressure
  9. customThe obtained residue was purified by silica gel column chromatography (Kanto Chemical, commercial name Silica gel 60N, granular, neutral, 0.040 mm-0.100 mm; n-heptane:ethyl acetate=4:1→3:1)

Sources & evidence

ORD record
ord-e50fa2c4a49c428d9ee309c19ff82da7
Source dataset
uspto-grants-2011_02
Patent number
US07884128B2

Reaction notes

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