Dimethylformamide → Ethyl 8-formylindolizine-5-carboxylate

HRID 1037080Notes

Reaction equation

HRID 1037080 reaction equation
FC(F)(F)S(O[C:7]1[C:15]2[N:11]([CH:12]=[CH:13][CH:14]=2)[C:10]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:9][CH:8]=1)(=O)=O.[SiH](CC)(CC)CC.CN([CH:33]=[O:34])C>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH:33]([C:7]1[C:15]2[N:11]([CH:12]=[CH:13][CH:14]=2)[C:10]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:9][CH:8]=1)=[O:34]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 12052TriethylsilaneHCID 86685512Ethyl 8-(((trifluoromethyl)sulfonyl)oxy)indolizine-5-carboxylate

Product 1

HCID 86685519Ethyl 8-formylindolizine-5-carboxylateYield 39%

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Conditions

Temperature
60 °C

Procedure

To a solution of ethyl 8-(((trifluoromethyl)sulfonyl)oxy)indolizine-5-carboxylate (4 g, 11.87 mmol) in DMF (1200 mL) was added TEA (3.6 g, 35.61 mmol), Et3SiH (4.14 g, 35.61 mmol) and Pd(dppf)2Cl2 (0.9 g, 10 mol %) under N2. The reaction mixture was stirred at 60° C. under CO (50 psi) overnight. The mixture was concentrated and to the residue were added EA and water, washed with brine, dried and concentrated and purified by column to give product ethyl 8-formylindolizine-5-carboxylate (1 g, yield 39%). 1H NMR (400 MHz, DMSO-d6): δ 10.15 (s, 1H), 8.61 (s, 1H), 7.76 (m, 1H), 7.63 (m, 1H), 7.37 (m, 1H), 7.10 (m, 1H), 4.46 (q, 2H), 1.39 (t, 3H) ppm.

Workup

  1. concentrationThe mixture was concentrated and to the residue
  2. additionwere added EA and water
  3. washwashed with brine
  4. customdried
  5. concentrationconcentrated
  6. custompurified by column

Sources & evidence

ORD record
ord-0286f9f51638497b9363d15aa042d32a
Source dataset
uspto-grants-2013_10
Patent number
US08546357B2

Reaction notes

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