Nitrogen → HCID 25139189, compound

HRID 1669109Notes

Reaction equation

HRID 1669109 reaction equation
[CH2:1]([Sn](CCCC)(CCCC)CCCC)[CH:2]=[CH2:3].N#N.[Si:19]([O:26][CH2:27][CH:28]1[CH2:42][C:41]2[C:30](=[CH:31][C:32]3[N+:37]([O-:38])=[N:36][C:35](I)=[N:34][C:33]=3[CH:40]=2)[CH2:29]1)([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20]>COCCOC.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>[CH2:3]([C:35]1[N:36]=[N+:37]([O-:38])[C:32]2[CH:31]=[C:30]3[C:41]([CH2:42][CH:28]([CH2:27][O:26][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20])[CH2:29]3)=[CH:40][C:33]=2[N:34]=1)[CH:2]=[CH2:1]

Participants

6

Reactant 3

HCID 947NitrogenHCID 90628AllyltributylstannaneHCID 25139184HCID 25139184, compound

Product 1

HCID 25139189HCID 25139189, compoundYield 99.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Allyltributyltin (4.35 mL, 14.1 mmol) and Pd(PPh3)4 (0.72 g, 0.64 mmol) were added to a N2-purged, stirred solution of iodide 133 (5.88 g, 12.9 mmol) in DME (80 mL) at 20° C. and the reaction mixture was stirred at reflux temperature under N2 for 8 h. The reaction mixture was cooled and partitioned between EtOAc and brine. The organic layer was separated, dried, and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-5%) of EtOAc/pet. ether, to give alkene 137 (4.75 g, 99%) as a yellow solid: mp (EtOAc/pet. ether) 49-52° C.; 1H NMR δ 8.23 (s, 1H, H-9), 7.74 (s, 1H, H-5), 6.17-6.24 (m, 1H, CH), 5.20-5.34 (m, 2H, CH2), 3.75-3.80 (m, 2H, CH2), 3.59-3.67 (m, 2H, CH2O), 3.13-3.25 (m, 2H, CH2), 2.92-3.04 (m, 2H, CH2), 2.72-2.84 (m, 1H, H-7), 0.87 [s, 9H, SiC(CH3)3], 0.04 [s, 6H, Si(CH3)2]; 13C NMR δ 164.1, 154.1, 148.3, 147.6, 133.0, 132.4, 123.0, 118.2, 114.5, 65.4, 42.0, 41.7, 35.8, 35.5, 25.8 (3), 18.3, −5.41 (2); HRMS (FAB+) calcd for C20H30N3O2Si (MH+) m/z 372.2107, found 372.2110. Anal. calcd for C20H29N3O2Si.¼H2O: C, 63.9; H, 7.9; N, 11.2. Found: C, 63.9; H, 7.7; N, 10.8%.

Workup

  1. custompurged
  2. temperatureat reflux temperature under N2 for 8 h
  3. temperatureThe reaction mixture was cooled
  4. custompartitioned between EtOAc and brine
  5. customThe organic layer was separated
  6. customdried
  7. customthe solvent evaporated
  8. customThe residue was purified by chromatography
  9. washeluting with a gradient (0-5%) of EtOAc/pet. ether

Sources & evidence

ORD record
ord-b853f1e434234abd8568e618e7b86132
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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