Sodium Carbonate → 3alpha-Acetoxy-17-(3-pyridyl)-5alpha-androst-16-ene

HRID 53185

Reaction equation

HRID 53185 reaction equation
C(B(CC)[C:4]1[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=1)C.FC(F)(F)S(OC1[C@]2(CC[C@H]3[C@@H](CCC4[C@]3(C)CCCC4)[C@@H]2CC=1)C)(=O)=O.[C:39]([O:42][C@@H:43]1[CH2:60][CH2:59][C@@:58]2([CH3:61])[C@@H:45]([CH2:46][CH2:47][C@@H:48]3[C@@H:57]2[CH2:56][CH2:55][C@@:53]2([CH3:54])[C@H:49]3[CH2:50][CH2:51][C:52]2=O)[CH2:44]1)(=[O:41])[CH3:40].C(=O)([O-])[O-].[Na+].[Na+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:39]([O:42][C@@H:43]1[CH2:60][CH2:59][C@@:58]2([CH3:61])[C@@H:45]([CH2:46][CH2:47][C@@H:48]3[C@@H:57]2[CH2:56][CH2:55][C@@:53]2([CH3:54])[C@H:49]3[CH2:50][CH:51]=[C:52]2[C:4]2[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=2)[CH2:44]1)(=[O:41])[CH3:40]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 101996Androsterone acetateHCID 6428513-(Diethylboryl)pyridineHCID 86750687Androst-16-en-17-yl trifluoromethanesulphonate

Product 1

HCID 99779013alpha-Acetoxy-17-(3-pyridyl)-5alpha-androst-16-eneYield 82%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

The method followed that described in Example 1, using in step (b) diethyl(3-pyridyl)borane (1.41 g, 9.6 mmol), 3,,-acetoxy- 5,,-androst-16-en-17-yl trifluoromethanesulphonate (3.44 g, 7.4 mmol), prepared from the 3α-acetoxy-5α-androstan-17-one by the method of step (a), THF (40 ml), bis(triphenylphosphine)palladium(II) chloride (52 mg, 0.07 mmol), and aqueous sodium carbonate (2M, 15 mmol). Chromatography, on elution with light petroleum-diethyl ether (2:1), afforded the title compound (2.39 g, 82%), 1H-NMR (CDCl3) inter alia δ 0.85(3H,s,19-CH3), 1.01(3H,s, 18-CH3), 2.06(3H,s,CH3CO2), 5.02(1H,m,3β-H), 6.00(1H,m, 16-H), 7.24(1H,m,Py 5-H), 7.68(1H,m,Py 4-H), 8.47(1H,m,Py 6-H), 8.63(1H,m,Py 2-H); MS m/z 393 (M+).

Workup

  1. washChromatography, on elution with light petroleum-diethyl ether (2:1)

Sources & evidence

ORD record
ord-c2cf415c4f4346d4bd48626a33c87a40
Source dataset
uspto-grants-1997_04
Patent number
US05618807

Linked notes

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