Nitrogen → HCID 54026644, compound

HRID 1456010Notes

Reaction equation

HRID 1456010 reaction equation
[OH:1][C:2]1([CH3:40])[CH:26]=[C:25]2[C@:20]([CH3:38])([CH2:21][CH2:22][C@H:23]([O:27][Si](C(C)C)(C(C)C)C(C)C)[CH2:24]2)[C@@H:19]2[C@@H:3]1[C@H:4]1[C@:16]([CH3:39])([CH2:17][CH2:18]2)[C@@H:7]([C@H:8]([CH3:15])[CH2:9][CH2:10][C:11]([O:13][CH3:14])=[O:12])[CH2:6][CH2:5]1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.N#N>>[OH:27][C@H:23]1[CH2:22][CH2:21][C@@:20]2([CH3:38])[C:25](=[CH:26][C:2]([OH:1])([CH3:40])[C@@H:3]3[C@@H:19]2[CH2:18][CH2:17][C@@:16]2([CH3:39])[C@H:4]3[CH2:5][CH2:6][C@@H:7]2[C@H:8]([CH3:15])[CH2:9][CH2:10][C:11]([O:13][CH3:14])=[O:12])[CH2:24]1

Participants

4

Reactant 3

HCID 947NitrogenHCID 2724141Tetrabutylammonium FluorideHCID 57164245HCID 57164245, compound

Product 1

HCID 54026644HCID 54026644, compoundYield 60.4%

Procedure

A mixture of methyl 7-hydroxy-7-methyl-3β-triisopropylsilyloxychol-5-en-24-oate (6) (4.67 g, 8.22 mmoles) and tetrabutylammonium fluoride (1.0M in THF, 49 ml) was heated at 65° in a N2 atmosphere for 30 min. Most of the THF was removed in vacuo. The residue was dissolved in EtOAc (90 ml) and washed with H2O (two times) and saturated brine. The aqueous phases were back-extracted with EtOAc. The combined EtOAc extracts were dried (MgSO4). Evaporation in vacuo and flash chromatography on silica gel with 7% methanol-CH2Cl2 gave 2.08 g of 8 as a yellow-brown foam. NMR (CDCl3) indicated a mixture of 7-isomers: d 0.70 (two peaks, 18-Me); 3.66 (CO2Me); Further elution gave 0.50 g of the tertiary alcohol 7 as a mixture of 7-isomers. NMR (CDCl3): δ 0.70 (two peaks, 18-Me); 1.20 (CMe2OH).

Workup

  1. customMost of the THF was removed in vacuo
  2. dissolutionThe residue was dissolved in EtOAc (90 ml)
  3. washwashed with H2O (two times) and saturated brine
  4. extractionThe aqueous phases were back-extracted with EtOAc
  5. dry with materialThe combined EtOAc extracts were dried (MgSO4)
  6. customEvaporation in vacuo and flash chromatography on silica gel with 7% methanol-CH2Cl2

Sources & evidence

ORD record
ord-27d35a61fb244d148afff7b16c25a88c
Source dataset
uspto-grants-1998_12
Patent number
US05843953

Reaction notes

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