Water → 5beta-Cholane-3alpha,7alpha,24-triol

HRID 1464251Notes

Reaction equation

HRID 1464251 reaction equation
[CH3:1][C@@H:2]([C@@H:9]1[C@@:13]2([CH3:29])[CH2:14][CH2:15][C@@H:16]3[C@@:21]4([CH3:27])[CH2:22][CH2:23][C@@H:24]([OH:26])[CH2:25][C@H:20]4[CH2:19][C@@H:18]([OH:28])[C@H:17]3[C@@H:12]2[CH2:11][CH2:10]1)[CH2:3][CH2:4][C:5](OC)=[O:6].O>C1COCC1>[OH:26][C@@H:24]1[CH2:23][CH2:22][C@@:21]2([CH3:27])[C@H:20]([CH2:19][C@@H:18]([OH:28])[C@@H:17]3[C@@H:16]2[CH2:15][CH2:14][C@@:13]2([CH3:29])[C@H:12]3[CH2:11][CH2:10][C@@H:9]2[C@H:2]([CH3:1])[CH2:3][CH2:4][CH2:5][OH:6])[CH2:25]1

Participants

4

Reactant 2

HCID 962WaterHCID 11069533Methyl chenodeoxycholate

Product 1

HCID 52840605beta-Cholane-3alpha,7alpha,24-triol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A suspension of LiA1H4 (0.15 g, 3 mols. equiv.) in dry THF (25 ml) was stirred under nitrogen whilst standing in an ice/methanol bath. Methyl chenodeoxycholate (5c) (0.5 g, 1.2 mmol) in dry THF (30 ml) was then added dropwise and the resultant mixture stirred at ambient temperature overnight. Water was then introduced carefully to the mixture until all the excess LiA1H4 had been destroyed. The resultant mixture was acidified with 2M HCl and extracted into EtOAc (3×). The combined organic extracts were washed with water (2×), dried and evaporated to give a white foam (0.47 g. 100%). Recrystallisation of 0.27 g from dichloromethane afforded pure 3α,7α,24-trihydroxy-50-cholane (7c)3 (0.16 g, 59%): m.p. 116°-118° C. [Lit. 9a 150° C.; also reported as an amorphous solid9b ]; 1H nmr (90 MHz; CDCl3 /DMSO d 6) δ0.64 (3H, s, 18-CH3), 0.88 (3H, s, 19-CH3), 2.9-3.2 (2H, s (exchanges on adding D2O], OH's, 3.1-3.6 (1H, m, 3β-H), 3.4-3.6 (2H, t[broadened), 24-CH2), 3.6-4.0 (1H, m[exchanges on adding D2O], OH), 3.7-3.9 (1H, m, 7β-H); IR (KBr) 3420 (OH's) cm-1 ; MS: Found m/z 378.3130; C24H42O3 (M) requires m/z 378.3134.

Workup

  1. customwhilst standing in an ice/methanol bath
  2. customhad been destroyed
  3. extractionextracted into EtOAc (3×)
  4. washThe combined organic extracts were washed with water (2×)
  5. customdried
  6. customevaporated
  7. customto give a white foam (0.47 g. 100%)
  8. customRecrystallisation of 0.27 g from dichloromethane afforded pure 3α,7α,24-trihydroxy-50-cholane (7c)3 (0.16 g, 59%)
  9. customLit. 9a 150° C.
  10. addition1H nmr (90 MHz; CDCl3 /DMSO d 6) δ0.64 (3H, s, 18-CH3), 0.88 (3H, s, 19-CH3), 2.9-3.2 (2H, s (exchanges on adding D2O], OH's, 3.1-3.6 (1H, m, 3β-H), 3.4-3.6 (2H
  11. additiont[broadened), 24-CH2), 3.6-4.0 (1H, m[exchanges on adding D2O], OH), 3.7-3.9 (1H, m, 7β-H)

Sources & evidence

ORD record
ord-8fc65d3f2fea455295ca199f4e3acbdc
Source dataset
uspto-grants-1994_04
Patent number
US05304551

Reaction notes

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