Pyridine → 17beta-(1-Oxo-3-methylbutyl)-6-azaandrost-4-en-3-one

HRID 1077595Notes

Reaction equation

[C:1]([C@H:4]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:23]([CH2:24][CH2:25][C@:5]12[CH2:6]C(O)=O)[C@:21]1([CH3:22])[C:16](=[CH:17][C:18](=[O:26])[CH2:19][CH2:20]1)[N:15](C(C)(C)C)[CH2:14]3)(O)=[O:2].N1C=CC=CC=1.S(Cl)(Cl)=O.[CH2:41]([Mg]Br)[CH:42]([CH3:44])[CH3:43]>C1(C)C=CC=CC=1.CN(C)C=O>[O:2]=[C:1]([C@H:4]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:23]([CH2:24][CH2:25][C@:5]12[CH3:6])[C@:21]1([CH3:22])[C:16](=[CH:17][C:18](=[O:26])[CH2:19][CH2:20]1)[NH:15][CH2:14]3)[CH2:41][CH:42]([CH3:44])[CH3:43]

Participants

Conditions

Temperature: 0 °C

Procedure

Alternatively, a solution of 17β-carboxy-6-t-butylcarboxy-6-azaandrost-4-en-3-one (260 mg, 0.62 mmol), example 3, Part F, is dissolved in toluene (10 mL) and treated with pyridine (3 eq) and catalytic dimethylformamide, cooled to 0° C., and thionyl chloride added (80 μL, 1.10 mmol). The reaction is then allowed to warm to room temperature and is stirred for 1 hr. The solids are then removed by filtration, the solution concentrated, the resulting crude acid chloride dissolved in THF (6 mL), CuL added (120 mg, 0.62 mmol), cooled to -78° C. and treated with isobutylmagnesium bromide (2.0M in diethyl ether, 0.5 mL, 1 mmol). The reaction is allowed to warm to room temperature, stirred for 30 min and is worked up as in Part C above to give 17β-(1-oxo-3-methylbutyl)-6-azaandrost-4-en-3-one.

Workup

temperatureto warm to room temperature
customThe solids are then removed by filtration
concentrationthe solution concentrated
dissolutionthe resulting crude acid chloride dissolved in THF (6 mL)
additionCuL added (120 mg, 0.62 mmol)
temperaturecooled to -78° C.
temperatureto warm to room temperature
stirringstirred for 30 min

Sources & evidence

ORD record: ord-c09b852582a342669d6e1f5208b9bc31
Source dataset: uspto-grants-1996_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05543406

Reaction notes

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