Nitrogen → (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-boronophenyl)-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]chrysene-3a-carboxylic acid

HRID 2405521

Reaktionsgleichung

Reaktionsgleichung von HRID 2405521
C([O:8][C:9]([C@:11]12[CH2:45][CH2:44][C@@H:43]([C:46]([CH3:48])=[CH2:47])[C@@H:12]1[C@@H:13]1[C@@:26]([CH3:29])([CH2:27][CH2:28]2)[C@@:25]2([CH3:30])[C@@H:16]([C@:17]3([CH3:42])[C@@H:22]([CH2:23][CH2:24]2)[C:21]([CH3:32])([CH3:31])[C:20]([C:33]2[CH:38]=[CH:37][C:36]([B:39]([OH:41])[OH:40])=[CH:35][CH:34]=2)=[CH:19][CH2:18]3)[CH2:15][CH2:14]1)=[O:10])C1C=CC=CC=1.N#N.B(Br)(Br)Br>C(Cl)Cl>[B:39]([C:36]1[CH:37]=[CH:38][C:33]([C:20]2[C:21]([CH3:32])([CH3:31])[C@H:22]3[C@:17]([CH3:42])([CH2:18][CH:19]=2)[C@@H:16]2[C@:25]([CH3:30])([C@@:26]4([CH3:29])[C@H:13]([CH2:14][CH2:15]2)[C@H:12]2[C@H:43]([C:46]([CH3:48])=[CH2:47])[CH2:44][CH2:45][C@:11]2([C:9]([OH:10])=[O:8])[CH2:28][CH2:27]4)[CH2:24][CH2:23]3)=[CH:34][CH:35]=1)([OH:41])[OH:40]

Komponenten

5

Edukt 3

HCID 947NitrogenHCID 25134Boron tribromideHCID 67775377(4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((benzyloxy)carbonyl)-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)boronic acid

Produkt 1

HCID 67775165(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-boronophenyl)-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]chrysene-3a-carboxylic acidAusbeute 26,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A −78° C. solution of (4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((benzyloxy)carbonyl)-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)boronic acid (0.200 g, 0.308 mmol) in DCM (3 mL) was purged with N2(g). Boron tribromide (1M solution in DCM) (1.079 mL, 1.079 mmol) was added dropwise. The resulting yellow reaction mixture was stirred at −78° C. for 1 h. The cold bath was removed and H2O (5 mL) was added to quench the reaction. The resulting white paste was filtered and washed with H2O. The crude material was dissolved in THF and DCM loaded onto a silica gel column and eluted with 1:1 hexanes:EtOAc to give 93 mg crude material which was further purified by reverse phase HPLC to give (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-boronophenyl)-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]chrysene-3a-carboxylic acid (45.2 mg, 24.15%) as a white solid. 1H NMR (500 MHz, DMSO-d6) δ 12.09 (br. s., 1H), 7.97 (br. s., 2H), 7.68 (d, J=7.9 Hz, 2H), 7.04 (d, J=7.9 Hz, 2H), 5.18 (d, J=4.6 Hz, 1H), 4.70 (s, 1H), 4.57 (s, 1H), 3.02-2.90 (m, 1H), 2.33-2.23 (m, 1H), 2.12 (d, J=6.4 Hz, 1H), 2.05 (dd, J=17.2, 6.3 Hz, 1H), 1.80 (d, J=7.3 Hz, 2H), 1.69-1.66 (m, 1H), 1.65 (s, 3H), 1.56 (t, J=11.3 Hz, 1H), 1.50 (br. s., 1H), 1.45-1.36 (m, 8H), 1.33-1.28 (m, 1H), 1.23 (br. s., 1H), 1.21-1.12 (m, 3H), 1.02-0.98 (m, 1H), 0.97 (s, 3H), 0.93 (s, 6H), 0.87 (s, 3H), 0.86 (s, 3H).

Aufarbeitung

  1. customThe cold bath was removed
  2. additionH2O (5 mL) was added
  3. customto quench
  4. customthe reaction
  5. filtrationThe resulting white paste was filtered
  6. washwashed with H2O
  7. dissolutionThe crude material was dissolved in THF
  8. washeluted with 1:1 hexanes
  9. customEtOAc to give 93 mg crude material which
  10. customwas further purified by reverse phase HPLC

Quellen und Nachweise

ORD-Eintrag
ord-a367894a561f41939cca96c0047d4b86
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08802661B2

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