Triphenylphosphine → S-3-(tert-butoxycarbonylamino)propyl ethanethioate

HRID 1968490Notes

Reaction equation

HRID 1968490 reaction equation
O[CH2:2][CH2:3][CH2:4][NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9].[S:13]1C=CC=C1CC(O)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:41][CH:42]([O:44]C(/N=N/C(OC(C)C)=O)=O)C>C(Cl)Cl>[C:42](=[O:44])([S:13][CH2:2][CH2:3][CH2:4][NH:5][C:6]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:12])[CH3:41]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 159702-Thiopheneacetic acidHCID 3838134tert-butyl N-(3-hydroxypropyl)carbamateHCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 14194548S-3-(tert-butoxycarbonylamino)propyl ethanethioateYield 75%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

tert-Butyl 3-hydroxypropylcarbamate (3.22 g, 18.37 mmol) in 100 ml of DCM at 0° C. was added thiolacetic acid (2.0 ml, 26.73 mmol) and triphenylphosphine (7.0 g, 26.73 mmol) under Ar. After stirred at 0° C. for 15 min, DIAD (6.0 ml, 28.93) was added. The mixture was stirred at 0° C. for 2 h then RT overnight. The mixture was concentrated, diluted with 120 ml of EtAc/Hexane (1:2), filtered through celite. The solution was washed with NaHCO3 (conc.)/NaCl (conc.) and 1 M NaH2PO4 respectively, dried over MgSO4, filtered, evaporated and purified on SiO2 chromatography eluted with EtAc/Hexane (1:7 to 1:6) to afford 3.22 g (75%) of the title compound. 1H NMR (CDCl3) 3.09 (t, 2H, J=6.5 Hz), 2.84 (t, 2H, J=6.9 Hz), 2.27 (s, 3H), 1.69 (dt, 2H, J=6.8, 13.5 Hz),1.38 (s, 9H); 13C NMR 196.35, 156.16, 79.50, 39.26, 30.79, 30.24, 28.61, 26.44; MS m/z+ 256.0 (M+Na).

Workup

  1. stirringThe mixture was stirred at 0° C. for 2 h
  2. customRT overnight
  3. concentrationThe mixture was concentrated
  4. additiondiluted with 120 ml of EtAc/Hexane (1:2)
  5. filtrationfiltered through celite
  6. washThe solution was washed with NaHCO3 (conc.)/NaCl (conc.) and 1 M NaH2PO4 respectively
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. customevaporated
  10. custompurified on SiO2 chromatography
  11. washeluted with EtAc/Hexane (1:7 to 1:6)

Sources & evidence

ORD record
ord-3be6f833d9aa4243871b821787cc6afd
Source dataset
uspto-grants-2013_04
Patent number
US08426402B2

Reaction notes

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