Phenyl vinyl sulfone → methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(phenylsulfonyl)ethyl)amino)-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)cyclohexa-1,3-dienecarboxylate

HRID 1401038Notes

Reaction equation

HRID 1401038 reaction equation
[NH2:1][C@:2]12[CH2:37][CH2:36][C@@H:35]([C:38]([CH3:40])=[CH2:39])[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([CH3:34])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]2[CH2:29][CH2:28][C:27]([C:30]([O:32][CH3:33])=[O:31])=[CH:26][CH:25]=2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1.[CH:41]([S:43]([C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)(=[O:45])=[O:44])=[CH2:42]>C1(C)C=CC=CC=1>[CH3:20][C@:17]12[C@@:16]3([CH3:21])[C@@H:7]([C@:8]4([CH3:34])[C@@H:13]([CH2:14][CH2:15]3)[C:12]([CH3:22])([CH3:23])[C:11]([C:24]3[CH2:29][CH2:28][C:27]([C:30]([O:32][CH3:33])=[O:31])=[CH:26][CH:25]=3)=[CH:10][CH2:9]4)[CH2:6][CH2:5][C@@H:4]1[C@H:3]1[C@H:35]([C:38]([CH3:40])=[CH2:39])[CH2:36][CH2:37][C@:2]1([NH:1][CH2:42][CH2:41][S:43]([C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)(=[O:44])=[O:45])[CH2:19][CH2:18]2

Participants

4

Reactant 2

HCID 79664Phenyl vinyl sulfoneHCID 86692397methyl 4-((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)cyclohexa-1,3-dienecarboxylate

Product 1

HCID 86692398methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(phenylsulfonyl)ethyl)amino)-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)cyclohexa-1,3-dienecarboxylateYield 38.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

Methyl 4-((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)cyclohexa-1,3-dienecarboxylate (200 mg, 0.366 mmol) and (vinylsulfonyl)benzene (80 mg, 0.476 mmol) were dissolved in toluene (1 mL). The solution was warmed to 90° C. for 9 hours. The crude reaction mixture was applied onto a 12 gm silica gel column, purified with 0-10% ethyl acetate/hexanes as eluent to afford the title compound as a white solid (100 mg, 0.14 mmole, 38.2%). MS: m/e 714.53 (M+H)+, 2.46 min (method 2). 1H NMR (400 MHz, CHLOROFORM-d) δ 8.03-7.89 (m, 2H), 7.73-7.66 (m, 1H), 7.66-7.57 (m, 2H), 7.08-7.01 (m, 1H), 5.83 (d, J=5.5 Hz, 1H), 5.30 (d, J=1.8 Hz, 1H), 4.70 (d, J=2.5 Hz, 1H), 4.65-4.55 (m, 1H), 3.82-3.71 (m, 3H), 3.42-3.24 (m, 2H), 3.03-2.86 (m, 1H), 2.86-2.70 (m, 1H), 2.56-2.40 (m, 3H), 2.40-2.26 (m, 1H), 2.09-2.00 (m, 1H), 1.98-1.85 (m, 1H), 1.85-1.73 (m, 2H), 1.71-1.67 (m, 3H), 1.67-1.38 (m, 7H), 1.37-1.11 (m, 12H), 1.10-1.07 (m, 3H), 1.04-1.01 (m, 3H), 0.98 (d, J=3.3 Hz, 3H), 0.97-0.94 (m, 3H), 0.92-0.89 (m, 3H).

Workup

  1. customThe crude reaction mixture
  2. custompurified with 0-10% ethyl acetate/hexanes as eluent

Sources & evidence

ORD record
ord-fb526b02a58b4f069f3ad9192073faf6
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

Loading…