Trifluoromethanesulfonate → (2R)-2-[(R)-3-benzyloxytetradecanoylamino]-5-(hept-6-enyl)amino-pentan-1-ol

HRID 1920603Notes

Reaction equation

HRID 1920603 reaction equation
[O-]S(C(F)(F)F)(=O)=O.[NH2:9][CH2:10][CH2:11][CH2:12][C@@H:13]([NH:16][C:17](=[O:39])[CH2:18][C@H:19]([O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[CH2:14][OH:15]>C(Cl)Cl>[CH2:32]([O:31][C@H:19]([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[CH2:18][C:17]([NH:16][C@H:13]([CH2:12][CH2:11][CH2:10][NH:9][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH:18]=[CH2:17])[CH2:14][OH:15])=[O:39])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1

Participants

4

Reactant 2

HCID 2758875TrifluoromethanesulfonateHCID 11476040(2R)-5-amino-2-[(R)-3-benzyloxytetradecanoylamino]pentan-1-ol

Product 1

HCID 67493681(2R)-2-[(R)-3-benzyloxytetradecanoylamino]-5-(hept-6-enyl)amino-pentan-1-ol

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of freshly prepared triflate hereinabove (956 mg; 3.88 mmol.) in CH2Cl2 (10 ml) is added dropwise to a solution of (2R)-5-amino-2-[(R)-3-benzyloxytetradecanoylamino]pentan-1-ol (Section 1.1.2.) (1.69 g; 3.88 mmol) in CH2Cl2 (10 ml) and the mixture is stirred for 4 hours at room temperature under argon flow. After dilution with CH2Cl2, the reaction medium is successively washed with an aqueous saturated solution of NaHCO3 and with H2O. The organic layer thus obtained is dried over MgSO4 and concentrated under vacuum. By running a flash chromatography purification on a silica gel (15/1 CH2Cl2/MeOH eluent), there is recovered the desired secondary amine (862 mg; 43%) Rf=0.3 (8/1 CH2Cl2/MeOH). ES/MS: m/z ratio 532.0 [M+H]+. 1H-NMR (CDCl3, 250 MHz), δ in ppm: 7.2-7.4; 7.1; 5.8; 5.0; 4.6; 3.95; 3.5; 2.9; 2.5; 2.1; 1.9-1.5; 1.5-1.2; 0.9. 13C-NMR (CDCl3, 62.89 MHz), δ in ppm: 172.17; 138.28; 138.21; 128.39; 127.96; 127.71; 114.82; 76.80; 71.40; 63.81; 50.87; 48.30; 47.75; 41.57; 34.10; 33.39; 31.89; 29.66; 29.62; 29.33; 28.19; 28.03; 25.21 26.11; 25.78; 22.82; 22.66; 14.10. 1H-NMR (CDCl3, 250 MHz), δ in ppm: 7.2-7.4; 6.75; 5.8; 5.0; 4.5; 3.9; 3.5; 2.5; 2.0; 2.1; 1.7-1.2; 0.9. 13C-NMR (CDCl3, 62.89 MHz), δ in ppm: 172.77; 138.68; 138.14; 128.23; 127.72; 127.56; 114.22; 76.64; 71.37; 64.58; 51.45; 49.79; 49.37; 41.53; 33.90; 33.53; 31.77; 29.65; 29.20; 28.64; 28.57; 25.00; 26.68; 25.93; 22.53; 13.98 (ammonium salt and free base spectra, respectively).

Workup

  1. washAfter dilution with CH2Cl2, the reaction medium is successively washed with an aqueous saturated solution of NaHCO3 and with H2O
  2. customThe organic layer thus obtained
  3. dry with materialis dried over MgSO4
  4. concentrationconcentrated under vacuum
  5. customa flash chromatography purification on a silica gel (15/1 CH2Cl2/MeOH eluent), there
  6. customis recovered the desired secondary amine (862 mg; 43%) Rf=0.3 (8/1 CH2Cl2/MeOH)

Sources & evidence

ORD record
ord-d997037943264f57a6cf7b156bc01b08
Source dataset
uspto-grants-2012_05
Patent number
US08173133B2

Reaction notes

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