1,2-Dimethoxyethane → HCID 67777450, compound

HRID 406859Notes

Reaction equation

HRID 406859 reaction equation
[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(OC)=O)[CH2:4][CH2:3]2.B([C:45]1[CH:46]=[C:47]([CH:51]=[CH:52][CH:53]=1)[C:48]([OH:50])=[O:49])(O)O.[C:54](=[O:57])([O-:56])[O-].[Na+].[Na+].[CH3:60]OCCOC>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>[CH3:60][O:56][C:54]([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]([CH3:21])([CH3:22])[C:14]([C:45]2[CH:46]=[C:47]([CH:51]=[CH:52][CH:53]=2)[C:48]([OH:50])=[O:49])=[CH:13][CH2:12]3)[CH2:9][CH2:8]1)=[O:57]

Participants

7

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 27339573-Carboxyphenylboronic acidHCID 86666256HCID 86666256, compound

Product 1

HCID 67777450HCID 67777450, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 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 (240 mg, 0.399 mmol), 3-boronobenzoic acid (133 mg, 0.799 mmol), sodium carbonate (212 mg, 1.997 mmol) and Pd(Ph3P)4 (46.2 mg, 0.040 mmol) in DME (2.000 ml) and water (2 ml) was heated to 100° C. for 3 hours. TLC and LCMS indicated starting material was consumed, and the desired product was formed. The reaction mixture was cooled to room temperature, neutralized with 1N HCl, extracted with ethyl acetate, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by biotage using ethyl acetate/hexanes (0-100%) ethyl acetate/hexanes to give the desired product 3-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(methoxycarbonyl)-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)benzoic acid as a white solid (120 mg, 50%). LCMS: m/e 571.47 (M−H)−, 3.91 min (method 5). 1H NMR (500 MHz, DMSO-D6) δ ppm 0.88 (d, J=5.19 Hz, 6H), 0.92 (s, 3H), 0.95 (s, 3H), 0.98 (s, 3H), 1.00-1.56 (m, 15H), 1.57-1.73 (m, 5H), 1.73-1.86 (m, 2H), 2.07 (dd, J=17.24, 6.26 Hz, 1H), 2.11-2.17 (m, 1H), 2.18-2.28 (m, 1H), 2.85-3.03 (m, 1H), 3.61 (s, 3H), 4.59 (s, 1H), 4.72 (d, J=1.83 Hz, 1H), 5.25 (d, J=4.58 Hz, 1H), 7.33 (d, J=7.32 Hz, 1H), 7.40 (t, J=7.63 Hz, 1H), 7.65 (s, 1H), 7.82 (d, J=7.93 Hz, 1H).

Workup

  1. customwas consumed

Sources & evidence

ORD record
ord-b00fe50293974f379920892dd0e0c100
Source dataset
uspto-grants-2014_06
Patent number
US08754068B2

Reaction notes

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