Ethyl diazoacetate → HCID 15838329, compound

HRID 1938923Notes

Reaction equation

HRID 1938923 reaction equation
[OH:1][C@H:2]1[CH2:7][CH2:6][C@H:5]2[C@H:8]3[C@H:18]([CH2:19][CH2:20][C@:3]12[CH3:4])[C@:16]1([CH3:17])[C@H:11]([N:12]([CH3:22])[C:13](=[O:21])[CH2:14][CH2:15]1)[CH2:10][CH2:9]3.[N+](=[CH:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])=[N-]>C(Cl)Cl.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[CH3:22][N:12]1[C:13](=[O:21])[CH2:14][CH2:15][C@@:16]2([CH3:17])[C@H:11]1[CH2:10][CH2:9][C@@H:8]1[C@@H:18]2[CH2:19][CH2:20][C@@:3]2([CH3:4])[C@H:5]1[CH2:6][CH2:7][C@@H:2]2[O:1][CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27]

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetateHCID 10171822HCID 10171822, compound

Product 1

HCID 15838329HCID 15838329, compound

Reagents, catalysts & solvents 2

HCID 152122Dirhodium tetraacetateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 17β-hydroxy-4-methyl-5α-4-azaandrostan-3-one (2.37 g, 7.75 mmole) in methylene chloride (50 ml) was added ethyl diazoacetate (5.5 g, 48 mmole) and rhodium diacetate dimer (50 mg) intermittently in small portions during 60 hours resulting in ca. 35% conversion to product. The mixture was passed through a flash silica gel column eluted with 1.5% MeOH in CH2Cl2 to give the semi-purified product which was repurified via another flash silica gel column eluted with 60-95% EtOAc in hexane to give the title product. (Rf=0.3/EtOAc) mp. 39°-41° C.

Workup

  1. customresulting in ca. 35% conversion to product
  2. washeluted with 1.5% MeOH in CH2Cl2
  3. customto give the semi-purified product which
  4. customwas repurified via another flash silica gel column
  5. washeluted with 60-95% EtOAc in hexane

Sources & evidence

ORD record
ord-34bdd60c3c2446ea92efb60c88720b60
Source dataset
uspto-grants-1997_12
Patent number
US05693809

Reaction notes

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