Triethylamine → rac-(1R*,4R*)-5-pyridin-3-yl-bicyclo[2.2.2]oct-5-en-2-one

HRID 220232Notes

Reaction equation

HRID 220232 reaction equation
O[C:2]1([C:11]2[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=2)[CH2:7][CH:6]2[CH2:8][CH2:9][CH:3]1[CH2:4][C:5]2=[O:10].CCN(CC)CC.S(Cl)(C)(=O)=O>C(Cl)Cl.CN(C1C=CN=CC=1)C>[N:13]1[CH:14]=[CH:15][CH:16]=[C:11]([C:2]2[CH:3]3[CH2:9][CH2:8][CH:6]([CH:7]=2)[C:5](=[O:10])[CH2:4]3)[CH:12]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 595560585-Hydroxy-5-pyridin-3-ylbicyclo[2.2.2]octan-2-one

Product 1

HCID 68412872rac-(1R*,4R*)-5-pyridin-3-yl-bicyclo[2.2.2]oct-5-en-2-oneYield 58.9%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 0.5 g of crude 5-hydroxy-5-pyridin-3-yl-bicyclo[2.2.2]octan-2-one (intermediate K3A.2) in 20 mL DCM were added 84 mg DMAP and 1.6 mL NEt3. The mixture was cooled to 0° C. before 0.53 mL of mesylchloride was added dropwise. The resulting suspension was stirred at 0° C. for 1 h and then overnight at rt. The reaction was quenched by the addition of sat. aq. NaHCO3 solution. The water phase was extracted with EtOAc. The combined organic phases were washed with brine, dried over MgSO4 and concentrated in vacuo. Purification by CC (EtOAc) yielded 0.27 g of rac-(1R*,4R*)-5-pyridin-3-yl-bicyclo[2.2.2]oct-5-en-2-one as yellow oil.

Workup

  1. additionwas added dropwise
  2. customovernight
  3. customat rt
  4. customThe reaction was quenched by the addition of sat. aq. NaHCO3 solution
  5. extractionThe water phase was extracted with EtOAc
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customPurification by CC (EtOAc)

Sources & evidence

ORD record
ord-0680476a69e44c449825614557159d79
Source dataset
uspto-grants-2012_06
Patent number
US08202885B2

Reaction notes

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