Dichloromethane → HCID 67413887, compound

HRID 70479Notes

Reaction equation

HRID 70479 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][CH2:10][CH:9]1[CH:13]=[CH:14][C:15](OCC)=[O:16])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(Cl)Cl.B(F)(F)F.CCOCC.CC(C[AlH]CC(C)C)C>CCOC(C)=O>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][CH2:10][CH:9]1[CH:13]=[CH:14][CH2:15][OH:16])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8000Boron trifluoride etherateHCID 14487Diisobutylaluminum hydrideHCID 53933727Ethyl 3-(1-Boc-2-pyrrolidinyl)acrylate

Product 1

HCID 67413887HCID 67413887, compoundYield 79.2%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

A 2 L, 3-necked round bottomed flask equipped with an overhead stirred was charged with 14 (67 g, 0.20 mol) and DCM (400 mL). The solution was cooled to −78° C. To this solution was slowly added boron trifluoride etherate (30 mL, 0.20 mol). The reaction mixture was stirred for 30 min. DIBAL (1 M in DCM, 600 mL, 0.6 mol) was added at a moderate rate. The solution was stirred at −78° C. for 2 h and then treated with EtOAc (100 mL) over 30 min to discharge remaining reagent. The reaction mixture was allowed to warm to −5° C. The reaction mixture was CAREFULLY quenched by the dropwise addition of 1 M HCl. The reaction mixture was diluted with DCM and H2O and made acidic to dissolve aluminum salts. The layers were separated and the organic phase was washed successively with dilute aqueous HCl, water, and brine. The DCM layer was dried over Na2SO4, filtered, and concentrated. The residue was purified by flash chromatography (SiO2, 25% to 80% EtOAc/hexane) to afford 15 as a yellow oil (36 g, 79%). [TLC analysis, 1:1 hexane/EtOAc, Rf(14)=0.8; Rf(15)=0.2]. 1H NMR (CDCl3, 300 MHz) δ5.73-5.52 (m, 2H), 4.39-4.16 (m, 1H), 4.15-4.04 (m, 2H), 3.46-3.25 (m, 2H), 2.92 (br s, 1H), 2.08-1.93 (m, 1H), 1.92-1.79 (m, 2H), 1.78-1.62 (m, 1H), 1.42 (s, 9H) ppm.

Workup

  1. customA 2 L, 3-necked round bottomed flask equipped with an overhead
  2. stirringThe reaction mixture was stirred for 30 min
  3. stirringThe solution was stirred at −78° C. for 2 h
  4. temperatureto warm to −5° C
  5. customThe reaction mixture was CAREFULLY quenched by the dropwise addition of 1 M HCl
  6. additionThe reaction mixture was diluted with DCM and H2O
  7. dissolutionto dissolve aluminum salts
  8. customThe layers were separated
  9. washthe organic phase was washed successively with dilute aqueous HCl, water, and brine
  10. dry with materialThe DCM layer was dried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe residue was purified by flash chromatography (SiO2, 25% to 80% EtOAc/hexane)

Sources & evidence

ORD record
ord-548a5b429707494f8f56bf6b01358fc5
Source dataset
uspto-grants-2014_09
Patent number
US08822525B2

Reaction notes

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