Hydrogen Peroxide → HCID 10635973, compound

HRID 2425784Notes

Reaction equation

HRID 2425784 reaction equation
[C:1]([O:5][C:6]([NH:8][C@:9]1([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:11][C@H:10]1[CH:12]=[CH2:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].B1C2CCCC1CCC2.[Na].[OH:29]O>C1COCC1.CCCCCC.CCOC(C)=O.C(O)(=O)C>[C:1]([O:5][C:6]([NH:8][C@:9]1([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:11][C@H:10]1[CH2:12][CH2:13][OH:29])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 5360545SodiumHCID 10658673Ethyl (1R,2S)-1-[[(1,1-dimethylethoxy)carbonyl]amino]-2-ethenylcyclopropanecarboxylate

Product 1

HCID 10635973HCID 10635973, compoundYield 70.3%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a solution of (1R,2S)-ethyl 1-(tert-butoxycarbonylamino)-2-vinylcyclopropanecarboxylate (15.3 g, 59.9 mmol) in THF (100 ml) was added 9-BBN (180 ml, 90 mmol) dropwise at 0° C. The formed solution was stirred at room temperature for 2 hr. The final solution was cooled back to 0° C. while 3 M acetic acid, sodium salt (180 ml, 540 mmol) was added. To this well stirred mixture, hydrogen peroxide (89 ml, 869 mmol) was added dropwise (Caution should be exercised since the addition was exothermic). The formed warm two layer mixture was stirred overnight. Separated the upper organic layer. The aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine. Dried over MgSO4, filtered, evaporated. The residue was purified by silica gel column, eluted with 4:1, 3:1, 2:1, then 3:2 Hexane-EtOAc to afford the desired product (1R,2S)-ethyl 1-(tert-butoxycarbonylamino)-2-(2-hydroxyethyl)cyclopropanecarboxylate (11.50 g, 42.1 mmol, 70.2% yield) as a viscous oil, which solidified upon standing on the bench. 1H NMR (CDCl3) δ 1.18-1.21 (m, 1H), 1.25 (t, J=7 Hz, 3H), 1.35-1.40 (m, 1H), 1.44 (s, 9H), 1.61-1.65 (m, 1H), 1.70-1.75 (m 1H), 1.91-1.98 (m, 1H), 3.61-3.65 (m, 1H), 3.71-3.75 (m, 1H), 4.10-4.21 (m, 2H), 5.17 (b, 1H).

Workup

  1. additionwas added
  2. additionwas added dropwise (Caution
  3. additionshould be exercised since the addition
  4. temperatureThe formed warm two layer mixture
  5. stirringwas stirred overnight
  6. customSeparated the upper organic layer
  7. extractionThe aqueous layer was extracted with EtOAc
  8. washThe combined organic layers were washed with brine
  9. dry with materialDried over MgSO4
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was purified by silica gel column
  13. washeluted with 4:1, 3:1, 2:1

Sources & evidence

ORD record
ord-8239310e3a274bb0a37d01238e90be2a
Source dataset
uspto-grants-2011_06
Patent number
US07964560B2

Reaction notes

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