Dimethylformamide → 1-(tert-Butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde

HRID 1994192Notes

Reaction equation

HRID 1994192 reaction equation
Br[C:2]1[CH:3]=[C:4]2[CH2:10][CH2:9][N:8]([Si:11]([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12])[C:5]2=[N:6][CH:7]=1.C([Li])(C)(C)C.CCCCC.CN([CH:31]=[O:32])C>CCOCC>[C:14]([Si:11]([CH3:13])([CH3:12])[N:8]1[C:5]2=[N:6][CH:7]=[C:2]([CH:31]=[O:32])[CH:3]=[C:4]2[CH2:10][CH2:9]1)([CH3:17])([CH3:16])[CH3:15]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8003PentaneHCID 587309295-Bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridineHCID 178418306HCID 178418306, compound

Product 1

HCID 587309341-(tert-Butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-5-carbaldehydeYield 103.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a stirred and cooled (−78° C.) solution of the bromide 4 (5.00 g, 15.96 mmol) in Et2O (92 mL) was added dropwise 1.5 M solution of tert-butyllithium in pentane (22.3 mL, 33.5 mmol). After 45 min additional stirring at −78° C., DMF (5.6 mL, 72.3 mmol) was added dropwise, and the mixture was allowed to slowly warm to r.t. After 20 h the mixture was partitioned between saturated aqueous NaHCO3 solution and CH2Cl2. The organic layer was separated, dried (MgSO4), and concentrated to afford the crude aldehyde 13 (4.32 g). 1H NMR (400 MHz; CDCl3) δ 0.32 (s, 6H), 0.92 (s, 9H), 3.02 (m, 2H), 3.70 (m, 2H), 7.55 (d, J=2.0 Hz, 1H), 8.16 (d, J=2.0 Hz, 1H), 9.61 (s, 1H).

Workup

  1. stirringAfter 45 min additional stirring at −78° C.
  2. customAfter 20 h the mixture was partitioned between saturated aqueous NaHCO3 solution and CH2Cl2
  3. customThe organic layer was separated
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-9277b8c30fda449fbac8eeb358589359
Source dataset
uspto-grants-2010_01
Patent number
US07652137B2

Reaction notes

Loading…