tert-butyl 7-chloro-3-iodo-1H-pyrrolo[2,3-c]pyridine-1-carboxylate → tert-butyl 3-(2-tert-butoxy-2-oxoethyl)-7-chloro-1H-pyrrolo[2,3-c]pyridine-1-carboxylate

HRID 513205Notes

Reaction equation

HRID 513205 reaction equation
[Cl:1][C:2]1[N:3]=[CH:4][CH:5]=[C:6]2[C:10](I)=[CH:9][N:8]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:7]=12.[C:19]([O:23][C:24](=[O:28])[CH2:25][Zn]Cl)([CH3:22])([CH3:21])[CH3:20]>C1COCC1.[Pd].C(P)(C)(C)C.C(P)(C)(C)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:19]([O:23][C:24](=[O:28])[CH2:25][C:10]1[C:6]2[C:7](=[C:2]([Cl:1])[N:3]=[CH:4][CH:5]=2)[N:8]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH:9]=1)([CH3:22])([CH3:21])[CH3:20]

Participants

6

Reactant 2

HCID 86720575tert-butyl 7-chloro-3-iodo-1H-pyrrolo[2,3-c]pyridine-1-carboxylateHCID 178451184HCID 178451184, compound

Product 1

HCID 86720576tert-butyl 3-(2-tert-butoxy-2-oxoethyl)-7-chloro-1H-pyrrolo[2,3-c]pyridine-1-carboxylateYield 80.1%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 57475661Bis[(1,1-dimethylethyl)phosphanyl]palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 7-chloro-3-iodo-1H-pyrrolo[2,3-c]pyridine-1-carboxylate (500 mg, 1.3 mmol), bis-(tert-butyl-phosphine) palladium (67.5 mg, 0.13 mmol), and palladium acetate (7.4 mg, 0.003 mmol) in THF (10 mL) was added (2-tert-butoxy-2-oxoethyl)(chloro)zinc (6.6 mL, 3.3 mmol, 0.5 M in diethyl ether). The mixture was then heated to 50 C overnight, cooled to r.t. and quenched by addition of MeOH (1 mL). EtOAc was added and the solution was extracted with 5% KHSO4. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The crude material was purified on silica (gradient elution, 0-25% EtOAc/hexanes) to yield the title product (382 mg). HRMS (ESI) calc (M+H)+=367.1419. found 367.1422.

Workup

  1. temperatureThe mixture was then heated to 50 C overnight
  2. customquenched by addition of MeOH (1 mL)
  3. additionEtOAc was added
  4. extractionthe solution was extracted with 5% KHSO4
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude material was purified on silica (gradient elution, 0-25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-789126c2baf14fc2a55f482d2db51a46
Source dataset
uspto-grants-2015_08
Patent number
US09102673B2

Reaction notes

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