Tributylstannane → HCID 117982176, compound

HRID 1776112Notes

Reaction equation

HRID 1776112 reaction equation
[C:1]([O:5][C:6](=[O:29])[NH:7][C@H:8]1[CH2:16][CH2:15][CH2:14][C@H:13]([CH2:17][CH2:18]Br)[C@@H:12]([O:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:11]([CH3:27])[O:10][C:9]1=[O:28])([CH3:4])([CH3:3])[CH3:2].CC(N=NC(C#N)(C)C)(C#N)C.CCCC[SnH](CCCC)CCCC.[F-].[K+]>C1(C)C=CC=CC=1.CC(C)=O>[C:1]([O:5][C:6](=[O:29])[NH:7][C@H:8]1[CH2:16][CH2:15][CH2:14][C@H:13]([CH2:17][CH3:18])[C@@H:12]([O:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C@H:11]([CH3:27])[O:10][C:9]1=[O:28])([CH3:2])([CH3:3])[CH3:4]

Participants

7

Reactant 4

HCID 5948Tributylstannane2×HCID 6547Azobisisobutyronitrile2×HCID 522689Potassium FluorideHCID 117982172HCID 117982172, compound

Product 1

HCID 117982176HCID 117982176, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-bromoethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate (408 mg, 0.867 mmol) and AIBN (14.24 mg, 0.087 mmol) in anhydrous toluene (8.7 mL) was added Bu3SnH (257 μl, 0.954 mmol), and the reaction was heated to 80° C. After 1 h, TLC (4:1 hexanes: acetone) still showed starting material. An additional 0.5 equivalents of Bu3SnH and 0.05 equiv AIBN were added and the reaction was stirred for an additional 1 h at 80° C. The reaction was cooled to room temperature, stirred with 10% aqueous potassium fluoride (KF) solution (7 mL) for 20 h, and partitioned between Et2O (20 mL) and sat. NaCl solution (20 mL). The phases were separated and the aqueous phase was extracted with Et2O (2×20 mL). The organic extracts were combined, dried over MgSO4, filtered and concentrated to provide a white solid, which was purified by column chromatography on SiO2 (5→20% acetone/hexanes) to provide the title compound as a white solid (295 mg, 87%): 1H NMR (400 MHz, CDCl3) δ 7.38-7.16 (m, 2H), 7.00-6.87 (m, 3H), 5.19-4.97 (m, 2H), 4.18 (t, J=8.8 Hz, 2H), 2.27 (dt, J=13.1, 6.7 Hz, 1H), 1.91-1.77 (m, 1H), 1.70-1.58 (m, 3H), 1.58-1.48 (m, 1H), 1.44 (s, 9H), 1.28 (d, J=6.5 Hz, 3H), 1.25-1.14 (m, 2H), 1.12-1.01 (m, 1H), 0.86 (t, J=7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 173.34, 159.68, 154.91, 129.58, 120.95, 115.40, 81.44, 79.86, 74.74, 53.00, 44.96, 34.20, 28.34, 27.85, 27.03, 26.85, 23.50, 18.74, 18.40, 17.53, 13.61, 11.86; ESIMS m/z 392.3 ([M+H]+), 414.3 ([M+Na]+).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. custompartitioned between Et2O (20 mL) and sat. NaCl solution (20 mL)
  3. customThe phases were separated
  4. extractionthe aqueous phase was extracted with Et2O (2×20 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto provide a white solid, which
  9. customwas purified by column chromatography on SiO2 (5→20% acetone/hexanes)

Sources & evidence

ORD record
ord-1c9738cfb4504553a8ac3145ef063891
Source dataset
uspto-grants-2016_02
Patent number
US09265253B2

Reaction notes

Loading…