Ethyl Acetate → HCID 86701797, compound

HRID 338636Notes

Reaction equation

HRID 338636 reaction equation
S(O[C@H:12]1[CH2:16][N:15]([C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[O:18])[C@H:14]([CH2:27]OS(C2C=CC(C)=CC=2)(=O)=O)[CH2:13]1)(C1C=CC(C)=CC=1)(=O)=O.[S-2:39].[Na+].[Na+].CCOC(C)=O>CS(C)=O>[C@H:12]12[CH2:13][C@H:14]([N:15]([C:17]([O:19][CH2:20][C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=3)=[O:18])[CH2:16]1)[CH2:27][S:39]2

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 14804Sodium SulfideHCID 14994792Phenylmethyl (2S,4R)-4-[[(4-methylphenyl)sulfonyl]oxy]-2-[[[(4-methylphenyl)sulfonyl]oxy]methyl]-1-pyrrolidinecarboxylate

Product 1

HCID 86701797HCID 86701797, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
110 °C

Procedure

(2S,4R)-benzyl 4-(tosyloxy)-2-((tosyloxy)methyl)pyrrolidine-1-carboxylate (10 g, 17.87 mmol) and sodium sulfide (1.125 mL, 26.8 mmol) were combined in DMSO (80 mL) in a 150 mL medium pressure flask. The reaction mixture was purged with N2 (g) and the resulting slurry was heated to 110° C. under a N2 (g) atmosphere. The reaction became deep blue immediately. After 17 h, the resulting black reaction mixture was cooled to rt, diluted with 1:1 EtOAc:Et2O (150 mL) and washed with H2O (100 mL). The aqueous layer was extracted with 1:1 EtOAc:Et2O (100 mL). The combined organic layer was washed with 1N HCl (100 mL), brine, dried over MgSO4, filtered and concentrated to give dark red viscous oil. The crude material was loaded onto a silica gel column (60 g) and eluted with 3:1 hex:EtOAc to give (1S,4S)-benzyl 2-thia-5-azabicyclo[2.2.1]heptane-5-carboxylate (2.7 g, 61% yield) as red viscous oil. LC/MS: m/e 250.0 (M+H)+, 2.22 min (method 3). 1H NMR (400 MHz, CHLOROFORM-d) δ 7.39-7.31 (m, 5H), 5.18-5.06 (m, 2H), 4.79-4.65 (m, 1H), 3.64 (d, J=7.8 Hz, 2H), 3.59 (br. s., 1H), 3.22-3.04 (m, 1H), 3.04-2.96 (m, 1H), 2.16 (t, J=10.0 Hz, 1H), 1.88 (d, J=10.3 Hz, 1H).

Workup

  1. customThe reaction mixture was purged with N2 (g)
  2. temperaturethe resulting black reaction mixture was cooled to rt
  3. additiondiluted with 1:1 EtOAc
  4. washEt2O (150 mL) and washed with H2O (100 mL)
  5. extractionThe aqueous layer was extracted with 1:1 EtOAc
  6. washThe combined organic layer was washed with 1N HCl (100 mL), brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give dark red viscous oil
  11. washeluted with 3:1 hex

Sources & evidence

ORD record
ord-6ad389e2d53d4131a6a454d2f552eaef
Source dataset
uspto-grants-2014_11
Patent number
US08889854B2

Reaction notes

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