Pyridine, hydrofluoride (1:1) → HCID 67588407, compound

HRID 1416787Notes

Reaction equation

HRID 1416787 reaction equation
[CH2:1]([O:4][C:5]([C:7]1([C:45]([O:47][CH2:48][CH:49]=[CH2:50])=[O:46])[O:11][C:10]2[CH:12]=[CH:13][C:14]([CH2:16][C@H:17]([N:19]([CH2:28][C@H:29]([O:37][Si](C(C)(C)C)(C)C)[C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([Cl:36])[CH:31]=3)[C:20]([O:22][CH2:23][C:24]([Cl:27])([Cl:26])[Cl:25])=[O:21])[CH3:18])=[CH:15][C:9]=2[O:8]1)=[O:6])[CH:2]=[CH2:3].F.N1C=CC=CC=1>C1COCC1>[CH2:48]([O:47][C:45]([C:7]1([C:5]([O:4][CH2:1][CH:2]=[CH2:3])=[O:6])[O:11][C:10]2[CH:12]=[CH:13][C:14]([CH2:16][C@H:17]([N:19]([CH2:28][C@@H:29]([C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([Cl:36])[CH:31]=3)[OH:37])[C:20]([O:22][CH2:23][C:24]([Cl:25])([Cl:27])[Cl:26])=[O:21])[CH3:18])=[CH:15][C:9]=2[O:8]1)=[O:46])[CH:49]=[CH2:50]

Participants

4

Reactant 2

HCID 64774Pyridine, hydrofluoride (1:1)2×HCID 54314994HCID 54314994, compound

Product 1

HCID 67588407HCID 67588407, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a 0° C. solution of 650 mg (0.82 mmol) 5-{(2R)-2-[[(2R)-2-(tert-butyl-dimethyl-siloxy)-2-(3-chloro-phenyl)-ethyl]-(2,2,2-trichloro-ethoxycarbonyl)-amino]-propyl}-benzo[1,3]dioxole-2,2-dicarboxylic acid diallyl ester and 20 mL THF was added 1.0 mL of HF·pyridine, and the reaction mixture was warmed to room temperature. After 22 h, TLC indicated that some starting material remained (Rf =0.62 (2/1 hexanes/EtOAc), and an additional 1.0 mL of HF·pyridine was added. After a total of 26 h, TLC indicated the disappearance of starting material and the formation of the title compound (Rf =0.28 (2/1 hexanes/EtOAc). The reaction mixture was slowly quenched with 30 mL of sat. aq. NaHCO3, extracted with 2×75 mL Et2O and then with 1×75 mL EtOAc. The combined organics were washed with 1×100 mL brine, dried over MgSO4, filtered and evaporated to a colorless oil. Flash chromatography on silica gel, eluting with hexanes/EtOAc (2/1), gave 460 mg (0.68 mmol, an 83% yield) of the title compound (Rf =0.28; 2/1 hexanes/EtOAc) as a colorless oil; 1H NMR (300 MHz, CDCl3): δ 1.20-1.37 (m, 3H), 2.60-2.78 (m, 2H), 2.80-2.91 (m, 1H), 2.98-3.18 (m, 1H), 3.23-3.40 (m, 1H), 3.41-3.54 (m, 2H), 4.10-4.26 (br m, 1H), 4.73-4.92 (5H), 5.22-5.40 (complex m, 4H), 5.81-5.98 (complex m, 2H), 6.62-6.87 (m, 4H), 7.17-7.41 (m, 3H); MS (ES) m/z (relative intensity): 700 (M+ +Na, 100).

Workup

  1. customAfter a total of 26 h, TLC

Sources & evidence

ORD record
ord-05e2e0a56af6415e90928dddc906454b
Source dataset
uspto-grants-1999_06
Patent number
US05914339

Reaction notes

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