Acetone → HCID 131719510, compound

HRID 1079261Notes

Reaction equation

HRID 1079261 reaction equation
[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])O[CH:8]([C:42]([CH3:64])=[CH:43][CH:44]2[CH2:49][CH2:48][C:47]([O:54][Si:55]([CH2:60][CH3:61])([CH2:58][CH3:59])[CH2:56][CH3:57])([CH2:50][CH2:51][CH:52]=C)[CH:46]([O:62][CH3:63])[CH2:45]2)[CH:7]([CH3:65])[CH:6]([O:66][Si:67]([C:70]([CH3:73])([CH3:72])[CH3:71])([CH3:69])[CH3:68])[CH2:5][C:4]1=[O:74])[CH3:2].C[N+]1([O-])CC[O:79]CC1.CC(C)=O.[OH2:87]>C1COCC1.OS([O-])(=O)=O.[Na+].O=[Os](=O)(=O)=O>[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:87][CH:8]([C:42]([CH3:64])=[CH:43][CH:44]2[CH2:49][CH2:48][C:47]([O:54][Si:55]([CH2:58][CH3:59])([CH2:56][CH3:57])[CH2:60][CH3:61])([CH2:50][CH2:51][CH:52]=[O:79])[CH:46]([O:62][CH3:63])[CH2:45]2)[CH:7]([CH3:65])[CH:6]([O:66][Si:67]([C:70]([CH3:71])([CH3:72])[CH3:73])([CH3:69])[CH3:68])[CH2:5][C:4]1=[O:74])[CH3:2]

Participants

8

Reactant 4

HCID 180Acetone2×HCID 962WaterHCID 82029Methyl morpholine oxideHCID 131719511HCID 131719511, compound

Product 1

HCID 131719510HCID 131719510, compound

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 8028TetrahydrofuranSolventHCID 516919Sodium BisulfateSolvent

Procedure

To a solution of 17-ethyl-1-hydroxy-12-[2'-(4"-triethylsilyloxy-4"-[but-3-en-1-yl]-3"-methoxycyclohexyl)-1'-methylvinyl]-14-t-butyl-dimethylsilyloxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (1gm, 0.9 mmole) in THF (50 mL) was added OsO4 (0.15 M in THF, 0.6 mL, 0.09 mmole) and N-methylmorpholine-N-oxide (0.21 gm, 1.8 mmole). The reaction mixture was stirred for 6 hr at room temperature while monitoring the reaction progress by TLC (1:4, acetone:hexanes). The reaction mixture was diluted with saturated NaHSO4 and partitioned between diethyl ether, CH2Cl2 and H2O. The aqueous layer was extracted once with diethyl ether and the combined organic fractions were washed with brine, dried over Na2SO4, filtered and evaporated in vacuo. The crude diol product was dissolved in CH3OH (15 mL) and to it was added a solution NaIO4 (0.255 gm, 1.2 mmole) in H2O (5 mL). The reaction mixture was stirred at room temperature for 4 hours and the reaction progress was monitored by TLC (20% acetone:hexanes). The reaction was then partitioned between diethyl ether and H2O. Washed aqueous layer twice with ether and combined. The organic layer was washed with brine, dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified by chromatography (20% acetone:hexanes) to give the title compound (0.6 gm) MASS:(FAB) 1075 (M+ + Li).

Workup

  1. custompartitioned between diethyl ether, CH2Cl2 and H2O
  2. extractionThe aqueous layer was extracted once with diethyl ether
  3. washthe combined organic fractions were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. dissolutionThe crude diol product was dissolved in CH3OH (15 mL) and to it
  8. stirringThe reaction mixture was stirred at room temperature for 4 hours
  9. customThe reaction was then partitioned between diethyl ether and H2O
  10. washThe organic layer was washed with brine
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customThe crude product was purified by chromatography (20% acetone:hexanes)

Sources & evidence

ORD record
ord-962c1a2799544a33b38224ff8d2df04c
Source dataset
uspto-grants-1996_08
Patent number
US05550233

Reaction notes

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