HCID 68454232, compound → HCID 68452155, compound

HRID 2353593Notes

Reaction equation

HRID 2353593 reaction equation
[CH2:1]([C:3]1[S:4][C:5]([C:14]([OH:16])=O)=[C:6]2[C:10]=1[CH:9]1[C:11]([CH3:13])([CH3:12])[CH:8]1[CH2:7]2)[CH3:2].[Li][CH3:18]>C(OCC)C>[CH2:1]([C:3]1[S:4][C:5]([C:14](=[O:16])[CH3:18])=[C:6]2[C:10]=1[C@@H:9]1[C:11]([CH3:12])([CH3:13])[C@@H:8]1[CH2:7]2)[CH3:2]

Participants

4

Reactant 2

HCID 68454232HCID 68454232, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 68452155HCID 68452155, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of rac-(1aS,5aR)-2-ethyl-1,1-dimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid (5.9 g, 25.0 mmol) in diethyl ether (420 mL) MeLi (30 mL, 1.6 M solution in diethyl ether) is added at rt. The mixture is stirred at rt for 30 min before another portion of MeLi (6 mL) is added. Stirring is continued at rt for 1 h. The mixture is poured onto ice/water, the organic layer is separated, washed with 1 N aq. NaOH and brine, dried over Na2SO4, and filtered. The solvent is removed in vacuo and the crude product is purified by CC on silica gel eluting with hexane:EA 9:1 to give rac-1-((1aS,5aR)-2-ethyl-1,1-dimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalen-4-yl)-ethanone (3.7 g) as a pale yellow oil; LC-MS: tR=1.07 min, [M+1]+=235.31, 1H NMR (CDCl3): δ 2.98 (dd, J=5.9, 18.8 HZ, 1H), 2.83-2.70 (m, 3H), 2.40 (s, 3H), 1.94-1.87 (m, 2H), 1.27 (t, J=7.6 Hz, 3H), 1.12 (s, 3H), 0.71 (s, 3H).

Workup

  1. additionis added
  2. additionThe mixture is poured onto ice/water
  3. customthe organic layer is separated
  4. washwashed with 1 N aq. NaOH and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customThe solvent is removed in vacuo
  8. customthe crude product is purified by CC on silica gel eluting with hexane:EA 9:1

Sources & evidence

ORD record
ord-9a9e262162ff420e80ccbfaff011174a
Source dataset
uspto-grants-2010_07
Patent number
US07750040B2

Reaction notes

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