Phosphate → HCID 15429004, compound

HRID 2270536Notes

Reaction equation

HRID 2270536 reaction equation
CC([C@@H:5]1[C@:22]2([CH3:23])[C@H:8]([C@H:9]3[C@H:19]([CH2:20][CH2:21]2)[C@:17]2([CH3:18])[C:12](=[CH:13][C:14](=[O:24])[CH2:15][CH2:16]2)[CH2:11][CH2:10]3)[CH2:7][CH2:6]1)=CC.CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O.P([O-])([O-])([O-])=O>CC(C)=O>[CH3:23][C@:22]12[CH2:21][CH2:20][C@H:19]3[C@@H:9]([CH2:10][CH:11]=[C:12]4[C@:17]3([CH3:18])[CH2:16][CH2:15][C:14](=[O:24])[CH2:13]4)[C@@H:8]1[CH2:7][CH:6]=[CH:5]2

Participants

5

Reactant 3

HCID 1061PhosphateHCID 53703346HCID 53703346, compoundHCID 131709961Jones' reagent

Product 1

HCID 15429004HCID 15429004, compoundYield 104.8%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

This synthesis is depicted in FIG. 179. To a solution of alcohol 8 (545 mg, 2.0 mmol) in acetone (100 ml) at 0° C. under N2 was added rapidly Jones reagent (i, 1.5 ml, ca. 4 mmol). After 5 min., the mixture was poured into a dilute phosphate buffer (pH 7.2, 1200 ml) and extracted with ether. The extracts were washed with sat. aq. NaCl solution, dried (Na2SO4) and evaporated to give mainly Androsta-5,16-dien-3-one as an oil (567 mg). The crude product was dissolved in THF (7 ml) and reduced with lithium tris (1,2-dimethylpropyl) hydridoborate (c) at 0.55° as described for the preparation of 2. The crude product (530 mg) was chromatographed on silica gel (100 g) with CH2Cl2/ethyl acetate 4:1 to give 280 mg (51%) of pure a-alcohol 7 (eluted first) and 13 mg of 5 starting alcohol 8. A small sample of 7 was recrystallized from acetone/water at RT. M.p. 1380, [B]D −77.5° (c=1.2. -IR. (CDCl3): 3580m, 3430m, 1665w, 1590w, -1H-NMR. (360 MHz): 0.80 (s, 3 H); 1.06 (s, 3 H); 4.02 (m, w½8, 1 H); 5.44 (m, 1 H); 5.72 (m, 1 H); 5.86 (m, 1 H).

Workup

  1. extractionextracted with ether
  2. washThe extracts were washed with sat. aq. NaCl solution
  3. dry with materialdried (Na2SO4)
  4. customevaporated

Sources & evidence

ORD record
ord-3619a96f3246450eb5ebfc9634e11722
Source dataset
uspto-grants-2001_12
Patent number
US06331534B1

Reaction notes

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