Réaction #1552132

ord-3e8b9dcaf4a74818935d0e63253b0378

Équation de réaction

CC[C@H]1[C@@H](OC(=O)c2cccc(I)c2)[C@@H]2[C@H](CC[C@]3(C)[C@@H]([C@H](C)CCC(=O)OC)CC[C@@H]23)[C@@]2(C)CC[C@@H](OC(C)=O)C[C@@H]12
4
CC[C@H]1[C@@H](OC(=O)c2cccc(I)c2)[C@@H]2[C@H](CC[C@]3(C)[C@@H]([C@H](C)CCC(=O)OC)CC[C@@H]23)[C@@]2(C)CC[C@@H](OC(C)=O)C[C@@H]12
Methyl 3α-acetoxy-6α-ethyl-7α-(3′-iodobenzoyl)oxy-5β-cholan-24-oate
CC(C)(C)O
tBuOH
Clc1cccc(I)c1Cl
dichloroiodobenzene
→
CC[C@H]1[C@@H](OC(=O)c2cccc(I)c2)[C@@H]2[C@H](CC[C@@]3(C)[C@H]2CC[C@]3(Cl)[C@H](C)CCC(=O)OC)[C@@]2(C)CC[C@@H](OC(C)=O)C[C@@H]12
17-chloro
Rendement 92.0%
CC[C@H]1[C@@H](OC(=O)c2cccc(I)c2)[C@@H]2[C@H](CC[C@@]3(C)[C@H]2CC[C@]3(Cl)[C@H](C)CCC(=O)OC)[C@@]2(C)CC[C@@H](OC(C)=O)C[C@@H]12
Methyl 3α-acetoxy-6α-ethyl-7α-(3′-iodobenzoyl)oxy-17a-chloro-5β-cholan-24-oate
Rendement 92.0%

Réactifs

CC[C@H]1[C@@H](OC(=O)c2cccc(I)c2)[C@@H]2[C@H](CC[C@]3(C)[C@@H]([C@H](C)CCC(=O)OC)CC[C@@H]23)[C@@]2(C)CC[C@@H](OC(C)=O)C[C@@H]12
4
CC[C@H]1[C@@H](OC(=O)c2cccc(I)c2)[C@@H]2[C@H](CC[C@]3(C)[C@@H]([C@H](C)CCC(=O)OC)CC[C@@H]23)[C@@]2(C)CC[C@@H](OC(C)=O)C[C@@H]12
Methyl 3α-acetoxy-6α-ethyl-7α-(3′-iodobenzoyl)oxy-5β-cholan-24-oate
CC(C)(C)O
tBuOH
Clc1cccc(I)c1Cl
dichloroiodobenzene

Réactifs

Aucun

Solvants

ClCCl
CH2Cl2

Conditions de réaction

Conditions détaillées
See reaction.notes.procedure_details.

Traitement

  1. 1
    workup.ADDITIONwas added
  2. 2
    AutreThe mixture was deoxygenated for 3 min
  3. 3
    Autreby bubbling dry N2
  4. 4
    Autrewas photolyzed at 0° C.
  5. 5
    Autrefor 1 h
  6. 6
    AutreThe solvent was then evaporated under reduced pressure
  7. 7
    Autrethe residue was quickly purified by flash chromatography
  8. 8
    Lavageeluting with petroleum ether/EtOAc (8:2

Mode opératoire

To a solution of 4 (3.5 g, 4.95 mmol) in CH2Cl2 (280 ml) containing 0.3 M tBuOH (8.2 ml), dichloroiodobenzene (3.38 g, 12.4 mmol) was added. The mixture was deoxygenated for 3 min by bubbling dry N2. Then the mixture was photolyzed at 0° C. using a tungsten lamps (200 W) for 1 h. The solvent was then evaporated under reduced pressure and the residue was quickly purified by flash chromatography eluting with petroleum ether/EtOAc (8:2, v/v) to yield 3.35 g (4.52 mmol, 92%) of the 17-chloro derivative 5 as white solid.

Source

DOI: 10.6084/m9.figshare.5104873.v1Brevet: US08999964B2uspto-grants-2015_04