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

HRID 750379Notes

Reaction equation

HRID 750379 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 sulfur trioxide pyridine complex (53.0 g, 333 mmol) in dimethylsulfoxide (300 mL) was added to a solution of benzyl (5S)-5-{[t-butyloxycarbonyl]amino}-6-hydroxyhexylcarbamate (8.64 g, 34.4 mmol) and triethylamine (14.4 mL, 103 mmol) in dichloromethane (130 mL) 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 saturated aqueous sodium chloride (1000 mL). 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 1200 mL. 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 (2S)-6-{[(benzyloxy)carbonyl]amino}-2-[(tert-butoxycarbonyl)amino]hexanal (37.58 g. 93%). 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 saturated aqueous sodium chloride (1000 mL)
  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 1200 mL
  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-168b4a87afce4daeb2c0a97f355e9ff3
Source dataset
uspto-grants-2008_07
Patent number
US07402606B2

Reaction notes

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