Sodium hydride → HCID 86649362, compound

HRID 660384Notes

Reaction equation

HRID 660384 reaction equation
[H-].[Na+].[I-].[CH3:4][S+](C)(C)=O.[CH2:9]([O:16][CH2:17][C@H:18]([CH:31]([CH3:33])[CH3:32])[CH2:19][C@H:20]([NH:23][C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27])[CH:21]=[O:22])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>C1COCC1>[CH2:9]([O:16][CH2:17][C@H:18]([CH:31]([CH3:33])[CH3:32])[CH2:19][C@H:20]([NH:23][C:24](=[O:30])[O:25][C:26]([CH3:27])([CH3:28])[CH3:29])[C@@H:21]1[CH2:4][O:22]1)[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 57195734tert-butyl (2S,4S)-4-(benzyloxymethyl)-5-methyl-1-oxohexan-2-ylcarbamate

Product 1

HCID 86649362HCID 86649362, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A flame dried 250-mL, round-bottom flask was charged with sodium hydride (2.4 g, 60.0 mmol) and trimethyloxosulfonium iodide (13.2 g, 60 mmol). The flask was evacuated and refilled with N2, and dry DMSO (100 mL) was added. The mixture was stirred at rt for 1 h to afford a solution. A second 500-mL, round-bottom flask was charged with tert-butyl (2S,4S)-4-(benzyloxymethyl)-5-methyl-1-oxohexan-2-ylcarbamate (14 g, 40 mmol) and THF (150 mL). The flask was evacuated and refilled with N2, and the sulfur ylid solution prepared above was added through a cannula. The resulting mixture was stirred for 1 h at rt. The reaction mixture was quenched with brine and extracted with EtOAc (3×200 mL). The combined organic phases were dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel to afford tert-butyl (1S,3S)-3-(benzyloxymethyl)-4-methyl-1-((R)-oxiran-2-yl)pentylcarbamate (7.2 g, 50%). 1H NMR (400 MHz, CD3OD): δ 8.00 (s, 1H), 7.74 (d, J=8.4 Hz, 1H), 7.55 (m, 1H), 7.17 (m, 1H), 4.50 (m, 2H), 3.84-3.68 (m, 2H), 3.45 (m, 1H), 3.27 (s, 3H), 3.25-3.18 (m, 3H), 2.13 (m, 2H), 1.89-1.72 (m, 2H), 1.55 (m, 3H), 1.32-1.11 (m, 9H), 0.99-0.80 (m, 12H); MS: 364 (M++1)

Workup

  1. customA flame dried 250-mL, round-bottom flask
  2. customThe flask was evacuated
  3. additionrefilled with N2, and dry DMSO (100 mL)
  4. additionwas added
  5. customto afford a solution
  6. customThe flask was evacuated
  7. additionrefilled with N2
  8. customthe sulfur ylid solution prepared
  9. additionabove was added through a cannula
  10. stirringThe resulting mixture was stirred for 1 h at rt
  11. customThe reaction mixture was quenched with brine
  12. extractionextracted with EtOAc (3×200 mL)
  13. dry with materialThe combined organic phases were dried over Na2SO4
  14. filtrationfiltered
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-f7be2c1276c8457697c0fba836b35de1
Source dataset
uspto-grants-2011_12
Patent number
US08084485B2

Reaction notes

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