Potassium Carbonate → tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-ylmethyl)-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)benzoate

HRID 405102Notes

Reaction equation

HRID 405102 reaction equation
[NH2:1][CH2:2][C@:3]12[CH2:41][CH2:40][C@@H:39]([C:42]([CH3:44])=[CH2:43])[C@@H:4]1[C@@H:5]1[C@@:18]([CH3:21])([CH2:19][CH2:20]2)[C@@:17]2([CH3:22])[C@@H:8]([C@:9]3([CH3:38])[C@@H:14]([CH2:15][CH2:16]2)[C:13]([CH3:24])([CH3:23])[C:12]([C:25]2[CH:37]=[CH:36][C:28]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])=[CH:27][CH:26]=2)=[CH:11][CH2:10]3)[CH2:7][CH2:6]1.[CH2:45](C1C=C(C)C=CC=1S([O-])(=O)=O)[CH2:46]C1C=C(C)C=CC=1S([O-])(=O)=O.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.C1COCC1.C(Cl)Cl>[N:1]1([CH2:2][C@:3]23[CH2:41][CH2:40][C@@H:39]([C:42]([CH3:44])=[CH2:43])[C@@H:4]2[C@@H:5]2[C@@:18]([CH3:21])([CH2:19][CH2:20]3)[C@@:17]3([CH3:22])[C@@H:8]([C@:9]4([CH3:38])[C@@H:14]([CH2:15][CH2:16]3)[C:13]([CH3:24])([CH3:23])[C:12]([C:25]3[CH:37]=[CH:36][C:28]([C:29]([O:31][C:32]([CH3:33])([CH3:34])[CH3:35])=[O:30])=[CH:27][CH:26]=3)=[CH:11][CH2:10]4)[CH2:7][CH2:6]2)[CH2:46][CH2:45]1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 86676419tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aminomethyl)-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)benzoateHCID 867624794-Methyl-2-[2-(5-methyl-2-sulfonatophenyl)ethyl]benzenesulfonate

Product 1

HCID 86676422tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-ylmethyl)-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)benzoate

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
100 °C

Procedure

tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aminomethyl)-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)benzoate (200 mg, 0.667 mmol) was dissolved in DMF (10.00 mL) and THF (10.00 mL), ethane-1,2-diylbis(4-methylbenzenesulfonate) (247 mg, 0.667 mmol) was added, followed by K2CO3 (184 mg, 1.333 mmol) and the mixture was stirred at 100° C. until no starting material was detected by LCMS. An M+1=626.7 was observed by LC-MS. The reaction mixture was redissolved in CH2Cl2 (100 mL), washed by water (2×50 mL) and the organic layer was dried over sodium sulfate. The solvent was removed in vacuo and the resultant residue was purified by silica gel chromatography using a mixture of ethyl acetate/hexanes. A white foam was obtained (130 mg, 65%) LCMS: m/e 426.7 (MH+), 4.393 min (method 8). 1H NMR (400 MHz, CHLOROFORM-d) δ 7.90 (d, J=8.3 Hz, 2H), 7.24-7.11 (m, 2H), 5.30 (d, J=1.8 Hz, 1H), 4.70 (d, J=2.0 Hz, 1H), 4.60 (dd, J=2.3, 1.3 Hz, 1H), 2.56 (d, J=21.1 Hz, 1H), 2.44-2.33 (m, 1H), 2.26-2.05 (m, 3H), 2.04-1.89 (m, 1H), 1.86 (d, J=12.0 Hz, 1H), 1.82-1.58 (m, 18H), 1.56-1.37 (m, 7H), 1.35-1.21 (m, 6H), 1.19-1.06 (m, 6H), 1.03 (s, 3H), 0.99 (s, 3H), 0.93 (m, 6H)

Workup

  1. washwashed by water (2×50 mL)
  2. dry with materialthe organic layer was dried over sodium sulfate
  3. customThe solvent was removed in vacuo
  4. customthe resultant residue was purified by silica gel chromatography
  5. additiona mixture of ethyl acetate/hexanes
  6. customA white foam was obtained (130 mg, 65%) LCMS
  7. customm/e 426.7 (MH+), 4.393 min (method 8)

Sources & evidence

ORD record
ord-218b2479ef0449c09aaf3272ee5a7050
Source dataset
uspto-grants-2014_06
Patent number
US08748415B2

Reaction notes

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