Trimethylsilylacetylene → HCID 86661616, compound

HRID 1496935Notes

Reaction equation

HRID 1496935 reaction equation
I[C:2]1[CH:21]=[CH:20][C:5]([CH2:6][O:7][C@@H:8]2[CH2:13][O:12][C:11]3=[N:14][C:15]([N+:17]([O-:19])=[O:18])=[CH:16][N:10]3[CH2:9]2)=[CH:4][CH:3]=1.[C:22]([Si](C)(C)C)#[CH:23]>CN(C=O)C.CCN(CC)CC.[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:22]([C:2]1[CH:21]=[CH:20][C:5]([CH2:6][O:7][C@@H:8]2[CH2:13][O:12][C:11]3=[N:14][C:15]([N+:17]([O-:19])=[O:18])=[CH:16][N:10]3[CH2:9]2)=[CH:4][CH:3]=1)#[CH:23]

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 66707474HCID 66707474, compound

Product 1

HCID 86661616HCID 86661616, compoundYield 71.1%

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of iodide 43 (see Example 2C) (1.00 g, 2.49 mmol) and copper iodide (51 mg, 0.27 mmol) in DMF (10 mL) and Et3N (10 mL) was purged with N2. Ethynyltrimethylsilane (1.0 mL, 7.1 mmol) and PdCl2(PPh3)2 (93 mg, 0.13 mmol) were added and the mixture was stirred under N2 for 0.5 h. The resulting mixture was partitioned between EtOAc and water, the organic fraction was dried, and the solvent was removed. The residue was dissolved in THF (50 mL) and tetra-n-butylammonium fluoride (5 mL of a 1M solution in THF, 5 mmol) was added. The solution was stirred for 2 h and then concentrated. The residue was partitioned between EtOAc and water, and the organic fraction was dried and concentrated. Column chromatography of the residue on silca gel using gradient elution (1:1 hexanes EtOAc to EtOAc) gave (6S)-6-[(4-ethynylbenzyl)oxy]-2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine (129) (0.530 g, 71%) as a white solid: mp 162-164° C.; 1H NMR [(CD3)2SO] δ 8.01 (s, 1H), 7.45 (d, J=8.3 Hz, 2H), 7.32 (d, J=8.3 Hz, 2H), 4.62-4.71 (m, 3H), 4.47 (d, J=11.9 Hz, 1H), 4.20-4.30 (m, 3H), 4.14 (s, 1H). Anal. (C15H13N3O4) C, H, N.

Workup

  1. customwas purged with N2
  2. customThe resulting mixture was partitioned between EtOAc and water
  3. customthe organic fraction was dried
  4. customthe solvent was removed
  5. dissolutionThe residue was dissolved in THF (50 mL)
  6. additiontetra-n-butylammonium fluoride (5 mL of a 1M solution in THF, 5 mmol) was added
  7. stirringThe solution was stirred for 2 h
  8. concentrationconcentrated
  9. customThe residue was partitioned between EtOAc and water
  10. customthe organic fraction was dried
  11. concentrationconcentrated
  12. washelution (1:1 hexanes EtOAc to EtOAc)

Sources & evidence

ORD record
ord-da2671f75cc7406c9cba68d03d974ab1
Source dataset
uspto-grants-2015_12
Patent number
US09198913B2

Reaction notes

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