Diisopropylethylamine → HCID 131736795, compound

HRID 1486688Notes

Reaction equation

HRID 1486688 reaction equation
Cl[C:2](Cl)([O:4]C(=O)OC(Cl)(Cl)Cl)Cl.[OH:13][CH2:14][C:15]1[O:16][C:17](=[O:21])[O:18][C:19]=1[CH3:20].C(N(CC)C(C)C)(C)C.[NH2:31][C@@:32]1([C:45]([O:47][CH2:48][CH:49]=[CH2:50])=[O:46])[C@@H:37]([F:38])[CH2:36][C@@H:35]2[C@H:33]1[C@H:34]2[C:39]([O:41][CH2:42][CH:43]=[CH2:44])=[O:40]>C(Cl)(Cl)Cl.O1CCCC1.C(OCC)(=O)C>[F:38][C@H:37]1[CH2:36][C@@H:35]2[C@@H:33]([C@H:34]2[C:39]([O:41][CH2:42][CH:43]=[CH2:44])=[O:40])[C@:32]1([NH:31][C:2]([O:13][CH2:14][C:15]1[O:16][C:17](=[O:21])[O:18][C:19]=1[CH3:20])=[O:4])[C:45]([O:47][CH2:48][CH:49]=[CH2:50])=[O:46]

Participants

8

Reactant 4

HCID 81531DiisopropylethylamineHCID 94429TriphosgeneHCID 105108784-(Hydroxymethyl)-5-methyl-1,3-dioxol-2-oneHCID 131736794HCID 131736794, compound

Product 1

HCID 131736795HCID 131736795, compoundYield 115.8%

Reagents, catalysts & solvents 3

HCID 6212ChloroformSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of triphosgene (35 mg) in chloroform (4 mL), 4-(hydroxymethyl)-5-methyl-1,3-dioxol-2-one (45.9 mg) and a solution of N,N-diisopropylethylamine (0.18 mL) in tetrahydrofuran (4 mL) were added at room temperature. After the mixture was stirred at the same temperature for 30 minutes, a solution of (1S,2S,3S,5R,6S)-diallyl 2-amino-3-fluorobicyclo[3.1.0]hexane-2,6-dicarboxylate (D-13-3, 100 mg) in chloroform (4 mL) was added to the reaction mixture, and the mixture was stirred at the same temperature for 3 hours. To the reaction mixture, ethyl acetate was added, and the organic layer was washed once with water and once with brine, sequentially. After the organic layer was dried over anhydrous sodium sulfate, the insoluble was filtered, the filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel cartridge, hexane:ethyl acetate=90:10-70:30) to give (1S,2S,3S,5R,6S)-diallyl 3-fluoro-2-((((5-methyl-2-oxo-1,3-dioxol-4-yl)methoxy)carbonyl)amino)bicyclo[3.1.0]hexane-2,6-dicarboxylate (D-15-1, 60.0 mg) as a colorless amorphous.

Workup

  1. stirringthe mixture was stirred at the same temperature for 3 hours
  2. washthe organic layer was washed once with water and once with brine
  3. dry with materialAfter the organic layer was dried over anhydrous sodium sulfate
  4. filtrationthe insoluble was filtered
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customthe resulting residue was purified by silica gel column chromatography (silica gel cartridge, hexane:ethyl acetate=90:10-70:30)

Sources & evidence

ORD record
ord-9e28443da8434d26901f9ed183e317a9
Source dataset
uspto-grants-2016_08
Patent number
US09428483B2

Reaction notes

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