Allyl bromide → HCID 10788199, compound

HRID 1019292Notes

Reaction equation

HRID 1019292 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][O:17][CH3:18])[C:10]=1[I:19])=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[CH2:22](Br)[CH:23]=[CH2:24]>CN(C=O)C>[C:1]([O:5][C:6]([N:8]([C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][O:17][CH3:18])[C:10]=1[I:19])[CH2:24][CH:23]=[CH2:22])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 10523738HCID 10523738, compound

Product 1

HCID 10788199HCID 10788199, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 14 (141 mg, 0.37 mmol) in 12 mL anhydrous DMF was cooled to −10° C., and treated with NaH (22.3 mg, 0.55 mmol) in small portions. The resulting suspension was stirred for 15 min and treated with neat allyl bromide (0.16 mL, 1.56 mmol) in a slow dropwise manner. The reaction mixture was warmed to 25° C. and stirred for 1 h. The reaction mixture was quenched with the addition of 5% aqueous NaHCO3 (20 mL), and the aqueous layer was extracted with EtOAc (3×10 mL). The combined organic extracts were washed with H2O (5×10 mL), dried (Na2SO4), and condensed under reduced pressure to yield 15 as a 2:1 mixture of amide rotamers as a yellow oil. Flash chromatography (SiO2, 2.5×10 cm, 10% EtOAc/hexane) yielded 15 (149 mg, 96%) as a colorless oil: 1H NMR (CDCl3, 250 MHz) δ 7.17 (m, 1H), 6.95-6.78 (m, 2H), 5.98-5.84 (m, 1H), 5.21 (s, 2H), 5.09-5.03 (m, 2H), 4.46 (m, 1H), 3.50 (s, 3H), 1.50 and 1.31 (s, 9H); 13C NMR (CDCl3, 100 MHz) δ 157.5 and 157.0, 153.7, 146.1 and 145.7, 133.8 and 133.6, 129.5 and 129.0, 123.6 and 123.5, 117.6 and 117.1, 113.5 and 113.2, 95.0 and 94.1, 80.5 and 80.1, 56.4, 53.1, 51.9, 28.3 and 28.1; IR (film) νmax 2975, 1688, 1582, 1463, 1381, 1253, 1154, 1065, 990 cm−1; FABHRMS (NBA/NaI) m/z 420.0663 (C16H22INO4+H+ requires 420.0672).

Workup

  1. stirringstirred for 1 h
  2. customThe reaction mixture was quenched with the addition of 5% aqueous NaHCO3 (20 mL)
  3. extractionthe aqueous layer was extracted with EtOAc (3×10 mL)
  4. washThe combined organic extracts were washed with H2O (5×10 mL)
  5. customdried
  6. custom(Na2SO4), and condensed under reduced pressure

Sources & evidence

ORD record
ord-c38b1ec933f04cfb83783665971367ff
Source dataset
uspto-grants-2002_11
Patent number
US06486326B2

Reaction notes

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