Sodium Carbonate → 3-(4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(benzyloxycarbonyl)-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)phenyl)propanoic acid

HRID 406864

Reaktionsgleichung

Reaktionsgleichung von HRID 406864
[CH3:1][C@:2]12[C@@:19]3([CH3:20])[CH:10]([C@:11]4([CH3:31])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:22])([CH3:21])[C:14](OS(C(F)(F)F)(=O)=O)=[CH:13][CH2:12]4)[CH2:9][CH2:8][C@@H:7]1[C@H:6]1[C@H:32]([C:35]([CH3:37])=[CH2:36])[CH2:33][CH2:34][C@:5]1(C(OCC1C=CC=CC=1)=O)[CH2:4][CH2:3]2.B([C:51]1[CH:56]=[CH:55][C:54]([CH2:57][CH2:58][C:59]([OH:61])=[O:60])=[CH:53][CH:52]=1)(O)O.[C:62](=[O:65])([O-:64])[O-].[Na+].[Na+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:64][C:62]([C@:5]12[CH2:34][CH2:33][C@@H:32]([C:35]([CH3:37])=[CH2:36])[C@@H:6]1[C@@H:7]1[C@@:2]([CH3:1])([CH2:3][CH2:4]2)[C@@:19]2([CH3:20])[CH:10]([C@:11]3([CH3:31])[C@@H:16]([CH2:17][CH2:18]2)[C:15]([CH3:22])([CH3:21])[C:14]([C:51]2[CH:56]=[CH:55][C:54]([CH2:57][CH2:58][C:59]([OH:61])=[O:60])=[CH:53][CH:52]=2)=[CH:13][CH2:12]3)[CH2:9][CH2:8]1)=[O:65])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

7

Edukt 3

HCID 10340Sodium CarbonateHCID 38634844-(2-Carboxyethyl)benzeneboronic acidHCID 86666257(1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate

Produkt 1

HCID 677773223-(4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(benzyloxycarbonyl)-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)phenyl)propanoic acid

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 80711,2-DimethoxyethaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A mixture of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (100 mg, 0.148 mmol), 3-(4-boronophenyl)propanoic acid (43.0 mg, 0.222 mmol), Pd(Ph3P)4 (17.07 mg, 0.015 mmol) and sodium carbonate (78 mg, 0.739 mmol) in DME (1 mL) and Water (1 mL) was heated to 100° C. for 1.5 hours. LCMS indicated desired product was formed. The reaction mixture was cooled to the room temperature and neutralized to pH=4-5 using 1N HCl. The reaction mixture was extracted with ethyl acetate. The extracts were dried over Na2SO4, filtered through a celite pad and concentrated under reduced pressure. The residue was purified by 80-100% ethyl acetate/hexanes to give the desired product, 3-(4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(benzyloxycarbonyl)-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)phenyl)propanoic acid, as colorless oil (60 mg, 55%). LCMS: m/e 675.63 (M−H)−, 4.78 min (method 5). 1H NMR (500 MHz, CHLOROFORM-d) d ppm 0.82 (s, 3H), 0.89 (s, 3H), 0.90 (s, 3H), 0.95 (s, 3H), 0.97 (s, 3H), 0.99-1.73 (m, 17H), 1.69 (s, 3H), 1.80-1.97 (m, 2H), 2.04-2.11 (m, 1H), 2.19-2.37 (m, 2H), 2.62-2.73 (m, 2H), 2.93 (t, J=7.78 Hz, 2H), 3.04 (td, J=10.91, 4.73 Hz, 1H), 4.60 (s, 1H), 4.73 (d, J=2.14 Hz, 1H), 5.05-5.20 (m, 2H), 5.21-5.29 (m, 1H), 6.92-7.00 (m, 2H), 7.06 (d, J=7.63 Hz, 1H), 7.17 (t, J=7.48 Hz, 1H), 7.28-7.41 (m, 5H).

Quellen und Nachweise

ORD-Eintrag
ord-1250e0de1ed547b4ace1db300ae81ee2
Quelldatensatz
uspto-grants-2014_06
Patentnummer
US08754068B2

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