Trifluoroacetic acid → Ethyl 2-ethyl-4-(mercaptomethyl)cyclopentanecarboxylate

HRID 1969699Notes

Reaction equation

HRID 1969699 reaction equation
[CH2:1]([CH:3]1[CH2:7][C:6](=[CH2:8])[CH2:5][CH:4]1[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:2].C1([Si](C2C=CC=CC=2)(C2C=CC=CC=2)[SH:21])C=CC=CC=1.N(C(C)(C)C#N)=NC(C)(C)C#N.C(O)(C(F)(F)F)=O>C1(C)C=CC=CC=1.C(Cl)Cl>[CH2:1]([CH:3]1[CH2:7][CH:6]([CH2:8][SH:21])[CH2:5][CH:4]1[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:2]

Participants

7

Reactant 4

HCID 6422Trifluoroacetic acidHCID 6547AzobisisobutyronitrileHCID 621128TriphenylsilanethiolHCID 58558026Ethyl 2-ethyl-4-methylenecyclopentanecarboxylate

Product 1

HCID 58558085Ethyl 2-ethyl-4-(mercaptomethyl)cyclopentanecarboxylateYield 72.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

Ethyl 2-ethyl-4-methylenecyclopentanecarboxylate (0.720 g, 3.95 mmol), triphenylsilanethiol (1.329 g, 4.54 mmol) and 2,2′-azobis(2-methylpropionitrile) (0.195 g, 1.185 mmol) in toluene (3.95 mL) was heated at reflux for about 6 h. The reaction mixture was cooled to ambient temperature and then concd under reduced pressure. The material was purified by silica gel (40 g) chromatography eluting with a gradient of 0-10% EtOAc in heptane to give a colorless oil. The resulting oil was dissolved in DCM (4 mL) and TFA (1.52 mL, 19.7 mmol) was added. After stirring at ambient temperature for about 1 h, the solvent was removed under reduced pressure. The material was purified by silica gel (40 g) chromatography eluting with a gradient of 0-15% EtOAc in heptane to provide ethyl 2-ethyl-4-(mercaptomethyl)cyclopentanecarboxylate (0.620 g, 72%) as a colorless oil: 1H NMR (DMSO-d6) δ 4.13-4.01 (m, 2H), 2.50-2.30 (m, 3H), 2.24 (m, 1H), 2.15-1.87 (m, 3H), 1.66-1.54 (m, 1H), 1.50-1.37 (m, 2H), 1.31-1.23 (m, 2H), 1.17 (t, 3H), 0.83 (m, 3H).

Workup

  1. temperatureat reflux for about 6 h
  2. customThe material was purified by silica gel (40 g) chromatography
  3. washeluting with a gradient of 0-10% EtOAc in heptane
  4. customto give a colorless oil
  5. customthe solvent was removed under reduced pressure
  6. customThe material was purified by silica gel (40 g) chromatography
  7. washeluting with a gradient of 0-15% EtOAc in heptane

Sources & evidence

ORD record
ord-59969dae21544ec399c6c9726ce3d9fb
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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