(1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid → (1aS,5aR)-1-(1,1,2-Trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-ethanone

HRID 2366113Notes

Reaction equation

HRID 2366113 reaction equation
[CH3:1][C:2]1([CH3:15])[C@@H:4]2[CH2:5][C:6]3[C:10]([C@H:3]12)=[C:9]([CH3:11])[S:8][C:7]=3[C:12]([OH:14])=O.[Li][CH3:17]>CCOCC>[CH3:15][C:2]1([CH3:1])[C@@H:4]2[CH2:5][C:6]3[C:10]([C@H:3]12)=[C:9]([CH3:11])[S:8][C:7]=3[C:12](=[O:14])[CH3:17]

Participants

4

Reactant 2

HCID 57892448(1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acidHCID 178418348HCID 178418348, compound

Product 1

HCID 59380608(1aS,5aR)-1-(1,1,2-Trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-ethanoneYield 74.9%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of (1aS,5aR)-1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid (220 mg, 1.00 mmol) in Et2O (10 mL) is added a solution of MeLi (1.6 M, 1.4 mL, 2.10 mmol) in Et2O at such a pace that the reaction mixture is refluxing gently. Upon completion of the addition, stirring is continued at rt for 30 min. The reaction is quenched by adding sat. aq. NH4Cl (3 mL). The organic layer is separated, dried over Na2SO4 and the solvent is evaporated to give (1aS,5aR)-1-(1,1,2-trimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-ethanone (165 mg) as a pale yellow oil; LC-MS: tR=1.03 min, [M+1]+=221.20; 1H NMR (CDCl3): δ 3.00 (ddd, J=1.8, 4.7, 18.8 Hz, 1H), 2.80 (d, J=18.8 Hz, 1H), 2.38 (s, 6H), 1.93-1.90 (m, 2H), 1.14 (s, 3H), 0.74 (s, 3H).

Workup

  1. temperatureis refluxing gently
  2. additionUpon completion of the addition
  3. customThe reaction is quenched
  4. additionby adding sat. aq. NH4Cl (3 mL)
  5. customThe organic layer is separated
  6. dry with materialdried over Na2SO4
  7. customthe solvent is evaporated

Sources & evidence

ORD record
ord-8d29de5da5a342a3845d0bcee69c4359
Source dataset
uspto-grants-2014_04
Patent number
US08697732B2

Reaction notes

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