Triethylamine → Phenylmethyl N-[(5S)-5-[[(1,1-dimethylethoxy)carbonyl]amino]-6-oxohexyl]carbamate

HRID 1180742Notes

Reaction equation

HRID 1180742 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]([CH2:25][OH:26])[CH2:10][CH2:11][CH2:12][CH2:13][NH:14][C:15](=[O:24])[O:16][CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C>CS(C)=O.ClCCl>[CH2:17]([O:16][C:15]([NH:14][CH2:13][CH2:12][CH2:11][CH2:10][C@H:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH:25]=[O:26])=[O:24])[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

Participants

5

Reactant 2

HCID 8471TriethylamineHCID 10915530Boc-Lysinol(Z)

Product 1

HCID 11100590Phenylmethyl N-[(5S)-5-[[(1,1-dimethylethoxy)carbonyl]amino]-6-oxohexyl]carbamateYield 299.8%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 53.0 g (333 mmol) of sulfur trioxide pyridine complex in 300 mL of dimethylsulfoxide was added to a solution of 8.64 g (34.4 mmol) of benzyl (5S)-5-{[t-butyloxycarbonyl]amino}-6-hydroxyhexylcarbamate and 14.4 mL (103 mmol) of triethylamine in 130 mL of dichloromethane at 0° C. The cold bath was removed, and the reaction mixture was stirred for 23 h. It was then poured slowly into a mixture of ice and 1 L of saturated aqueous sodium chloride. The resulting mixture was extracted with three 600 mL portions of ether. The ether extracts were then combined, washed with three 150 mL portions of saturated aqueous sodium chloride, and concentrated to 1.2 L. The concentrated ether phase was further washed with three 200 mL aliquots of 5% aqueous citric acid, and a 200 mL portion of saturated aqueous sodium chloride. After drying over magnesium sulfate, volatiles were removed under vacuum to afford 37.58 g (93%) of (2S)-6-{[(benzyloxy)carbonyl]amino}-2-[(tert-butoxycarbonyl)amino]hexanal. 1H NMR (300 MHz, DMSO-d6) δ 9.44 (s, 1H), 7.46-7.23 (m, 6H), 5.02 (s, 2H), 3.85-3.75 (m, 1H), 3.07-2.93 (m, 2H), 1.77-1.60 (m, 1H), 1.56-1.23 (m, 5H), 1.41 (s, 9H).

Workup

  1. customThe cold bath was removed
  2. additionIt was then poured slowly into a mixture of ice and 1 L of saturated aqueous sodium chloride
  3. extractionThe resulting mixture was extracted with three 600 mL portions of ether
  4. washwashed with three 150 mL portions of saturated aqueous sodium chloride
  5. concentrationconcentrated to 1.2 L
  6. washThe concentrated ether phase was further washed with three 200 mL aliquots of 5% aqueous citric acid
  7. dry with materialAfter drying over magnesium sulfate, volatiles
  8. customwere removed under vacuum

Sources & evidence

ORD record
ord-0df64d79c1b54b8494b4ae89a3f1519e
Source dataset
uspto-grants-2007_10
Patent number
US07282512B2

Reaction notes

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