3beta-Benzyloxy-5-androsten-17-one → 3beta-Methyl-5alpha-androstan-17-one

HRID 861640Notes

Reaction equation

HRID 861640 reaction equation
O([C@:3]12[CH2:20][C@@H:19](O)[CH2:18][CH2:17][C@:16]1([CH3:22])[C@@H:15]1[C@H:6]([C@H:7]3[C@@:11]([CH2:13][CH2:14]1)([CH3:12])[C:10](=[O:23])[CH2:9][CH2:8]3)[CH:5]=[CH:4]2)O.[CH2:24](O[C@H]1CC[C@@]2(C)C(=CC[C@@H]3[C@@H]2CC[C@@]2(C)[C@H]3CCC2=O)C1)C1C=CC=CC=1.[H][H]>C(O)(=O)C.[Pd]>[CH3:24][C@H:19]1[CH2:18][CH2:17][C@@:16]2([CH3:22])[C@@H:3]([CH2:4][CH2:5][C@@H:6]3[C@@H:15]2[CH2:14][CH2:13][C@@:11]2([CH3:12])[C@H:7]3[CH2:8][CH2:9][C:10]2=[O:23])[CH2:20]1

Participants

6

Reactant 3

HCID 537649083beta-Benzyloxy-5-androsten-17-one2×HCID 566283895alpha-Hydroperoxy-3beta-hydroxyandrost-6-en-17oneHCID 178418361HCID 178418361, compound

Product 1

HCID 186376273beta-Methyl-5alpha-androstan-17-oneYield 80%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolvent

Procedure

Firstly an example of catalytic hydrogenation for the synthesis of 5α-androstanes from androst-5-enes is the synthesis of 3β-methyl-5α-androstan-17-one 2 from 3β-methylandrost-5-en-17-one 1. 3β-Methylandrost-5-en-17-one 1 (400 mg), prepared as described previously was dissolved in glacial acetic acid (80 ml). Palladium on carbon (10%, 100 mg) was added and the solution maintained under an atmosphere of hydrogen. When hydrogen uptake ceased, the solution was filtered through celite and evaporated to give solid which was recrystallized from methanol to yield 3β-methyl-5α-androstan-17-one, 2, (320 mg, 80% yield). MP 107°-108° C., 1H NMR (CDCl3) δ 0.86 (d, 3H, J-5 Hz, methyl at C-3), 0.85 (s, 3H, C-19 Me), 0.79 (s, 3H, C-18 Me).

Workup

  1. temperaturethe solution maintained under an atmosphere of hydrogen
  2. filtrationthe solution was filtered through celite
  3. customevaporated
  4. customto give solid which
  5. customwas recrystallized from methanol

Sources & evidence

ORD record
ord-99ae7be385aa4b57ab39496de1cbe74d
Source dataset
uspto-grants-1998_02
Patent number
US05714481

Reaction notes

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