Triethylborane → Tert-butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-ylcarbamate

HRID 1814009Notes

Reaction equation

HRID 1814009 reaction equation
[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[C:14](Cl)[N:13]=[C:12]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:31](B(CC)CC)[CH3:32]>CN(C=O)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]>[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[C:14]([CH2:31][CH3:32])[N:13]=[C:12]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 7357TriethylboraneHCID 10796Cesium carbonateHCID 86588266tert-Butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-chloropyridin-2-ylcarbamate

Product 1

HCID 69550702Tert-butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-ylcarbamate

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

tert-Butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-chloropyridin-2-ylcarbamate (11-4, 0.496 g, 1.33 mmol) was dissolved in 2 mL DMF. Dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct (0.087 g, 0.11 mmol), cesium carbonate (2.601 g, 7.98 mmol), and triethylborane (1M in hexanes) (3.190 mL, 3.19 mmol) were added and the solution was heated to 50° C. After 24 hours the reaction was allowed to cool to room temperature and was concentrated to afford a brown oil. The oil was filtered through celite and washed with CH2Cl2. The filtrate was concentrated to afford a light brown oil. The oil was purified by flash column chromatography (10:90 EtOAc/hexanes) to afford tert-butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-ylcarbamate as a light yellow oil. Free base: 1H NMR (CDCl3) δ 7.60 (s, 1H), 7.14 (bs, 1H), 6.91 (s, 1H), 4.71 (s, 2H), 2.68 (q, 2H, J=7.63 Hz), 1.51 (s, 9H), 1.25 (t, 3H, J=7.63 Hz), 0.95 (s, 9H), 0.10 (s, 6H).

Workup

  1. temperatureto cool to room temperature
  2. concentrationwas concentrated
  3. customto afford a brown oil
  4. filtrationThe oil was filtered through celite
  5. washwashed with CH2Cl2
  6. concentrationThe filtrate was concentrated
  7. customto afford a light brown oil
  8. customThe oil was purified by flash column chromatography (10:90 EtOAc/hexanes)

Sources & evidence

ORD record
ord-2a9044a548f049ffbf747b34239fdb2b
Source dataset
uspto-grants-2005_04
Patent number
US06875767B2

Reaction notes

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