HCID 54764960, compound → HCID 67777356, compound

HRID 2405514Notes

Reaction equation

HRID 2405514 reaction equation
[C:1]([CH2:4][CH2:5][NH:6][C:7]([C@:9]12[CH2:43][CH2:42][C@@H:41]([C:44]([CH3:46])=[CH2:45])[C@@H:10]1[C@@H:11]1[C@@:24]([CH3:27])([CH2:25][CH2:26]2)[C@@:23]2([CH3:28])[C@@H:14]([C@:15]3([CH3:40])[C@@H:20]([CH2:21][CH2:22]2)[C:19]([CH3:30])([CH3:29])[C:18]([C:31]2[CH:39]=[CH:38][C:34]([C:35]([OH:37])=[O:36])=[CH:33][CH:32]=2)=[CH:17][CH2:16]3)[CH2:13][CH2:12]1)=[O:8])([OH:3])=[O:2].C(N/C(=N/C(C)C)/O[CH2:53][CH2:54][Si:55]([CH3:58])([CH3:57])[CH3:56])(C)C>C1COCC1.CCOC(C)=O>[CH3:27][C@:24]12[C@@:23]3([CH3:28])[C@@H:14]([C@:15]4([CH3:40])[C@@H:20]([CH2:21][CH2:22]3)[C:19]([CH3:30])([CH3:29])[C:18]([C:31]3[CH:32]=[CH:33][C:34]([C:35]([O:37][CH2:53][CH2:54][Si:55]([CH3:58])([CH3:57])[CH3:56])=[O:36])=[CH:38][CH:39]=3)=[CH:17][CH2:16]4)[CH2:13][CH2:12][C@@H:11]1[C@H:10]1[C@H:41]([C:44]([CH3:46])=[CH2:45])[CH2:42][CH2:43][C@:9]1([C:7](=[O:8])[NH:6][CH2:5][CH2:4][C:1](=[O:3])[O:2][CH2:53][CH2:54][Si:55]([CH3:56])([CH3:57])[CH3:58])[CH2:26][CH2:25]2

Participants

5

Reactant 2

HCID 54764960HCID 54764960, compoundHCID 178457540HCID 178457540, compound

Product 1

HCID 67777356HCID 67777356, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(2-carboxyethylcarbamoyl)-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 (35 mg, 0.056 mmol) and (Z)-2-(trimethylsilyl)ethyl N,N′-diisopropylcarbamimidate (27.2 mg, 0.111 mmol) was refluxed in THF (1 mL) for 4 h. Then the mixture was placed at room temperature for 16 h. TLC showed no starting material and a new less polar product Rf=0.4 in 10% AcOEt/Hex. The solvent was removed in vacuo. The residue was dissolved in methylene chloride and purified in silica gel (0-10% AcOEt/Hex) to afford 2-(trimethylsilyl)ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-(3-oxo-3-(2-(trimethylsilyl)ethoxy)propylcarbamoyl)-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 (43 mg, 0.049 mmol, 89% yield) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.93 (d, J=8.28 Hz, 2H), 7.20 (d, J=8.03 Hz, 2H), 6.24 (t, J=6.02 Hz, 1H), 5.30 (d, J=4.77 Hz, 1H), 4.76 (d, J=1.51 Hz, 1H), 4.61 (s, 1H), 4.49-4.37 (m, 2H), 4.28-4.17 (m, 2H), 3.65-3.52 (m, 1H), 3.52-3.39 (m, 1H), 3.15 (td, J=10.85, 3.64 Hz, 1H), 2.63-2.43 (m, 3H), 2.11 (dd, J=17.19, 6.40 Hz, 1H), 2.02-1.90 (m, 2H), 1.80-1.04 (m, 22H), 1.70 (s, 3H), 1.01 (s, 3H), 1.00 (s, 3H), 0.98 (s, 3H), 0.93 (s, 6H), 0.10 (s, 9H), 0.06 (s, 9H).

Workup

  1. customThe solvent was removed in vacuo
  2. dissolutionThe residue was dissolved in methylene chloride
  3. custompurified in silica gel (0-10% AcOEt/Hex)

Sources & evidence

ORD record
ord-e1adbce0d99e4b39b1f2b3bf09fc1a49
Source dataset
uspto-grants-2014_08
Patent number
US08802661B2

Reaction notes

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