Acetone → 3-Phenylthio-6-(2-hydroxyprop-2-yl)-7-oxobicyclo[3.2.0]-hept-2-en-2-carboxylic Acid, Diphenylmethyl Ester

HRID 2164589Notes

Reaction equation

HRID 2164589 reaction equation
C[Si](C)(C)N[Si](C)(C)C.C([Li])CCC.[C:15]1([S:21][C:22]2[CH2:28][CH:27]3[CH:24]([C:25](=[O:29])[CH2:26]3)[C:23]=2[C:30]([O:32][CH:33]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)=[O:31])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[CH3:46][C:47]([CH3:49])=[O:48]>O1CCCC1.C(O)(=O)C>[C:15]1([S:21][C:22]2[CH2:28][CH:27]3[CH:24]([C:25](=[O:29])[CH:26]3[C:47]([OH:48])([CH3:49])[CH3:46])[C:23]=2[C:30]([O:32][CH:33]([C:40]2[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=2)[C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)=[O:31])[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1

Participants

7

Reactant 4

HCID 180AcetoneHCID 13838HexamethyldisilazaneHCID 134769553-Phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic Acid, Diphenylmethyl EsterHCID 178418339Butyllithium

Product 1

HCID 867399883-Phenylthio-6-(2-hydroxyprop-2-yl)-7-oxobicyclo[3.2.0]-hept-2-en-2-carboxylic Acid, Diphenylmethyl EsterYield 17.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of 60 μL of hexamethyl disilazane in 10 mL of dry tetrahydrofuran at 0° under argon was added dropwise 190 μL of butyllithium (1.37M in hexane). To this solution at -78° was added a solution of 106 mg of 3-phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid, diphenylmethyl ester, in 1 mL of tetrahydrofuran over a 3 min period. The reaction mixture was stirred for 10 min after which time 25 μL of acetone was added. After 20 min, 50 μL of acetic acid was added, the reaction mixture was evaporated to a small volume, and partitioned between methylene chloride and water. The organic layer was washed with brine, dried over sodium sulfate, and evaporated. The residue was subjected to preparative thin layer chromatography on a 20×20×0.2 cm silica gel plate eluted with ether-petroleum ether (1:2) to afford 21 mg (17.4%) of solid 3 -phenylthio-6-(2-hydroxyprop-2-yl)-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid, diphenylmethyl ester. IR (neat): 3400, 1765, 1685, 1545 cm-1 ; NMR (220 MHz; CDCl3): δ 1.17 (3H, s), 1.25 (1H, s), 1.32 (3H, s), 2.30 (1H, J=18, 3.5), 2.8-3.0 (2H, m), 3.11 (1H, dd, J=6, 3), 4.5 (1H, m), 6.93 (1H, s), and 7.2-7.6 (15H, m).

Workup

  1. additionwas added
  2. customthe reaction mixture was evaporated to a small volume
  3. custompartitioned between methylene chloride and water
  4. washThe organic layer was washed with brine
  5. dry with materialdried over sodium sulfate
  6. customevaporated
  7. washeluted with ether-petroleum ether (1:2)

Sources & evidence

ORD record
ord-bb67aa6cb4c640aab9524a9681f48c71
Source dataset
uspto-grants-1985_03
Patent number
US04505905

Reaction notes

Loading…