1,2-Dichloroethane → ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)bicyclo[3.1.0]hex-2-ene-6-carboxylate

HRID 1401033Notes

Reaction equation

HRID 1401033 reaction equation
[NH2:1][C@:2]12[CH2:38][CH2:37][C@@H:36]([C:39]([CH3:41])=[CH2:40])[C@@H:3]1[C@@H:4]1[C@@:17]([CH3:20])([CH2:18][CH2:19]2)[C@@:16]2([CH3:21])[C@@H:7]([C@:8]3([CH3:35])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]2[CH2:29][CH:28]4[CH:26]([CH:27]4[C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH:25]=2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Cl[CH2:51][CH2:52]Cl>C(#N)C>[N:1]1([C@:2]23[CH2:38][CH2:37][C@@H:36]([C:39]([CH3:41])=[CH2:40])[C@@H:3]2[C@@H:4]2[C@@:17]([CH3:20])([CH2:18][CH2:19]3)[C@@:16]3([CH3:21])[C@@H:7]([C@:8]4([CH3:35])[C@@H:13]([CH2:14][CH2:15]3)[C:12]([CH3:22])([CH3:23])[C:11]([C:24]3[CH2:29][CH:28]5[CH:26]([CH:27]5[C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH:25]=3)=[CH:10][CH2:9]4)[CH2:6][CH2:5]2)[CH2:52][CH2:51]1

Participants

5

Reactant 3

HCID 111,2-DichloroethaneHCID 62657Potassium Phosphate, TribasicHCID 86692392ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)bicyclo[3.1.0]hex-2-ene-6-carboxylate

Product 1

HCID 86692393ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)bicyclo[3.1.0]hex-2-ene-6-carboxylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
130 °C

Procedure

To a flame dried 75 mL thick-walled resealable vessel was placed ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)bicyclo[3.1.0]hex-2-ene-6-carboxylate (0.453 g, 0.809 mmol) and flame dried potassium phosphate (0.859 g, 4.05 mmol), followed by 1,2-dichloroethane (24 mL) and acetonitrile (12 mL). The reaction mixture was flushed with nitrogen, sealed, and warmed to 130° C. for 36 hours. The crude reaction mixture was cooled to room temperature and filtered through a short bed of silica gel, washed with ethyl acetate to obtain a very pale orange solution, it was evaporated to dryness. White solid was obtained (0.3 g, 0.512 mmole, 63.3%), and used as it is. MS: m/e 586.55 (M+H)+, 2.791 min.

Workup

  1. customTo a flame dried 75 mL thick-walled resealable vessel
  2. customThe reaction mixture was flushed with nitrogen
  3. customsealed
  4. customThe crude reaction mixture
  5. temperaturewas cooled to room temperature
  6. filtrationfiltered through a short bed of silica gel
  7. washwashed with ethyl acetate
  8. customto obtain a very pale orange solution, it
  9. customwas evaporated to dryness
  10. customWhite solid was obtained (0.3 g, 0.512 mmole, 63.3%)
  11. customm/e 586.55 (M+H)+, 2.791 min.

Sources & evidence

ORD record
ord-e400d7e2f988495abf0e92a78177019e
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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