Triphenylphosphine → 2-Bromo-5-[3-{[tert-butyl(dimethyl)silyl]oxy}-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)propoxy]pyridine

HRID 2066677Notes

Reaction equation

HRID 2066677 reaction equation
CCOC(/N=N/C(OCC)=O)=O.[Si:13]([O:20][CH2:21][CH:22]([CH2:25][O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])[CH2:23][OH:24])([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14].[Br:34][C:35]1[N:40]=[CH:39][C:38](O)=[CH:37][CH:36]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1>[Br:34][C:35]1[CH:36]=[CH:37][C:38]([O:24][CH2:23][CH:22]([CH2:25][O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:28])[CH3:29])[CH2:21][O:20][Si:13]([C:16]([CH3:17])([CH3:19])[CH3:18])([CH3:15])[CH3:14])=[CH:39][N:40]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 27628652-Bromo-5-hydroxypyridineHCID 5462977Diethyl azodicarboxylateHCID 110676353-(Tert-butyldimethylsilanyloxy)-2-(tert-butyldimethylsilanyloxymethyl)propan-1-ol

Product 1

HCID 866505502-Bromo-5-[3-{[tert-butyl(dimethyl)silyl]oxy}-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)propoxy]pyridineYield 97%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Diethylazodicarboxylate (3.445 mL, 22.2 mmol) was added dropwise to a stirred mixture of 3-{[tert-butyl(dimethyl)silyl]oxy}-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)-1-propanol (184) (reported by Kim et al., 2001, via silylation and hydroboration of 2-methylene-1,3-propanediol) (5.706 g, 17.1 mmol), 6-bromo-3-pyridinol (3.571 g, 20.5 mmol) and triphenylphosphine (5.386 g, 20.5 mmol) in anhydrous THF (55 mL) at 0° C. under N2. After stirring at 0° C. for 1 h, and then at room temperature for 41 h, the mixture was concentrated under reduced pressure and the residue was chromatographed on silica gel. Elution with 0-5% Et2O/petroleum ether firstly gave foreruns, and then further elution with 5% Et2O/petroleum ether gave 2-bromo-5-[3-{[tert-butyl(dimethyl)silyl]oxy}-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)propoxy]pyridine (185) (8.09 g, 97%) as a colourless oil; 1H NMR (CDCl3) δ 8.06 (d, J=3.0 Hz, 1H), 7.35 (dd, J=8.7, 0.3 Hz, 1H), 7.11 (dd, J=8.7, 3.2 Hz, 1H), 4.03 (d, J=5.9 Hz, 2H), 3.73 (dd, J=10.1, 5.7 Hz, 1H), 3.69 (dd, J=10.0, 6.0 Hz, 1H), 2.16 (sept, J=5.8 Hz, 1H), 0.88 (s, 18H), 0.03 (2 s, 12H); HRESIMS calcd for C21H41BrNO3Si2 m/z [M+H]+ 492.1783, 490.1803. found 492.1786, 490.1804.

Workup

  1. waitat room temperature for 41 h
  2. concentrationthe mixture was concentrated under reduced pressure
  3. customthe residue was chromatographed on silica gel
  4. washElution with 0-5% Et2O/petroleum ether firstly gave foreruns
  5. washfurther elution with 5% Et2O/petroleum ether

Sources & evidence

ORD record
ord-ff9ca3781dd84c53bcc40e1ad5c5e6d8
Source dataset
uspto-grants-2012_10
Patent number
US08293734B2

Reaction notes

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