Hydrochloric Acid → HCID 11742322, compound

HRID 1938936Notes

Reaction equation

HRID 1938936 reaction equation
[CH2:1]([C:3]1(O)[CH:27]=[C:26]2[C@:21]([CH3:29])([CH2:22][CH2:23][C@H:24]([OH:28])[CH2:25]2)[C@@H:20]2[C@@H:4]1[C@H:5]1[C@:17]([CH3:30])([CH2:18][CH2:19]2)[C@@H:8]([C@H:9]([CH3:16])[CH2:10][CH2:11][CH2:12][CH:13]([CH3:15])[CH3:14])[CH2:7][CH2:6]1)[CH3:2].C(OC)(=O)CCC#C.Cl>CS(C)=O.C(NC(C)C)(C)C.CC([O-])=O.CC([O-])=O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd+2]>[CH2:1]([C:3]1[C@@H:4]2[C@@H:20]([C@:21]3([CH3:29])[C:26]([CH:27]=1)=[CH:25][C:24](=[O:28])[CH2:23][CH2:22]3)[CH2:19][CH2:18][C@@:17]1([CH3:30])[C@H:5]2[CH2:6][CH2:7][C@@H:8]1[C@H:9]([CH3:16])[CH2:10][CH2:11][CH2:12][CH:13]([CH3:15])[CH3:14])[CH3:2]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 543061Methyl 4-pentynoateHCID 57243272HCID 57243272, compound

Product 1

HCID 11742322HCID 11742322, compoundYield 97.4%

Reagents, catalysts & solvents 3

HCID 84538Palladium(2+) acetate--triphenylphosphane (1/2/2)CatalystHCID 679Dimethyl SulfoxideSolventHCID 7912DiisopropylamineSolvent

Procedure

A mixture of 436 mg (1.0 mmole) of 4-methyl-17-triflluoromethylsulfonyloxy-4-aza-5α-androst-16-en-3-one (60) (Case 18730), 168 mg (1.5 mmoles) of methyl 4-pentynoate, 40 mg of bis(triphenylphosphine)palladium(II) acetate, 5 mg of cuprous iodide in 3.0 ml of DMSO and 3.0 ml of N,N-diisopropylamine was stirred at room temperature for 17 hrs. The dark reaction mixture was poured into 50 ml of 0.5M HCl and extracted with CH2Cl2 (3×). The combined extracts were washed with water (4×) and dried (MgSO4). Evaporation in vacuo and flash chromatography of the residue on silica gel with 6:1 CH2Cl2 -acetone gave 400 mg of enyne 61. The enyne was immediately hydrogenated in 20 ml of EtOH with 150 mg of 10% palladium on carbon catalyst under a hydrogen-filled balloon. After stirring at room temperature for 24 hrs, the reaction mixture was filtered through a bed of Celite., which was washed with EtOH (4×). The filtrate and washes were evaporated in vacuo and the residue flash chromatographed on silica gel with 5:1 CH2Cl2 to give 345 mg of methyl 4-methyl-3-oxo-21-nor-4-aza-5α-cholane-24-carboxylate (62).

Workup

  1. customThe dark reaction mixture
  2. extractionextracted with CH2Cl2 (3×)
  3. washThe combined extracts were washed with water (4×)
  4. dry with materialdried (MgSO4)
  5. customEvaporation in vacuo and flash chromatography of the residue on silica gel with 6:1 CH2Cl2 -acetone

Sources & evidence

ORD record
ord-70e39e3ff73a4203a0b582bcd35f5ae3
Source dataset
uspto-grants-1997_12
Patent number
US05693809

Reaction notes

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