Dimethylformamide → 3-(((tert-Butyldimethylsilyl)oxy)methyl)picolinonitrile

HRID 1473905Notes

Reaction equation

HRID 1473905 reaction equation
Br[C:2]1[C:7]([CH2:8][O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])=[CH:6][CH:5]=[CH:4][N:3]=1.[CH3:17][N:18](C=O)C>[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Si:10]([O:9][CH2:8][C:7]1[C:2]([C:17]#[N:18])=[N:3][CH:4]=[CH:5][CH:6]=1)([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 227250932-Bromo-3-((tert-butyldimethylsilyloxy)methyl)pyridine

Product 1

HCID 230926273-(((tert-Butyldimethylsilyl)oxy)methyl)picolinonitrileYield 82%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
120 °C

Procedure

A mixture of 2-bromo-3-((tert-butyldimethylsilyloxy)methyl)pyridine (30.1 g, 100.0 mmol, 1 eq.) and Zn(CN)2 (23.5 g, 200.0 mmol, 2.0 eq.) in DMF (100.0 mL) was purged with N2 for 5 min and added Pd(PPh3)4 (5.78 g, 5.0 mmol, 0.05 eq.). The mixture was heated at 120° C. for 2 h under N2, cooled, filtered, concentrated, and purified on silica gel using a mixture of EtOAc and hexanes as eluent to give 3-((tert-butyldimethylsilyloxy)methyl)picolinonitrile (20.4 g, 82%) as a colorless oil. LRMS (M+H+) m/z 249.1.

Workup

  1. customwas purged with N2 for 5 min
  2. temperaturecooled
  3. filtrationfiltered
  4. concentrationconcentrated
  5. custompurified on silica gel using
  6. additiona mixture of EtOAc and hexanes as eluent

Sources & evidence

ORD record
ord-34aad2e0235f4a508d63ec1e23207d26
Source dataset
uspto-grants-2015_04
Patent number
US09018210B2

Reaction notes

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