1,8-Diazabicyclo(5.4.0)undec-7-ene → Methyl 2-(5-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-7-yl)-2-diazoacetate

HRID 913918Notes

Reaction equation

HRID 913918 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9]([CH2:11][C:12]([O:14][CH3:15])=[O:13])[C:8]2[C:4](=[CH:5][N:6]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[N:7]=2)[CH:3]=1.C(NC1C=CC(S([N:37]=[N+:38]=[N-])(=O)=O)=CC=1)(=O)C.N12CCCN=C1CCCCC2>C(#N)C>[Cl:1][C:2]1[CH:10]=[C:9]([C:11](=[N+:37]=[N-:38])[C:12]([O:14][CH3:15])=[O:13])[C:8]2[C:4](=[CH:5][N:6]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:21])([CH3:23])[CH3:22])[N:7]=2)[CH:3]=1

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 51291854-Acetamidobenzenesulfonyl azideHCID 57545943Methyl 2-(5-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-7-yl)acetate

Product 1

HCID 76561042Methyl 2-(5-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-7-yl)-2-diazoacetate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of methyl 2-(5-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-7-yl)acetate (1.95 g, 5.49 mmol) and 4-acetamidobenzenesulfonyl azide (1.52 g, 6.32 mmol) in acetonitrile (11 mL) at 0° C. was added 1,8-Diazabicyclo[5.4.0]undec-7-ene (1.04 mL, 6.87 mmol) dropwise over 20 min. The ice bath was removed and stirring continued at room temperature for 1 h. The reaction was partitioned between water and ethyl acetate. The organics were washed with saturated sodium bicarbonate, dried over sodium sulfate, and concentrated. The resulting residue was purified by column chromatography (8%→25% ethyl acetate/n-hexane) to give 1.39 g (66%) as a yellow oil. 1H-NMR (CDC13, 500 MHz) δ 8.01 (s, 1H), 7.79 (d, J=1.5 Hz, 1H), 7.45 (d, J=1.8 Hz, 1H), 5.64 (s, 2H), 3.89 (s, 3H), 3.64 (t, J=8.2 Hz, 2H), 0.93 (t, J=8.4 Hz, 2H), −0.03 (s,9H; 13C NMR (126 MHz, CDCl3) δ ppm 165.9, 143.2, 128.7, 125.3, 123.1, 122.7, 122.5, 116.5, 116.4, 81.8, 67.9, 52.1, 17.8, −1.4.

Workup

  1. customThe ice bath was removed
  2. customThe reaction was partitioned between water and ethyl acetate
  3. washThe organics were washed with saturated sodium bicarbonate
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe resulting residue was purified by column chromatography (8%→25% ethyl acetate/n-hexane)
  7. customto give 1.39 g (66%) as a yellow oil

Sources & evidence

ORD record
ord-23c154ffd6f545e5a543a1bb2adafe6e
Source dataset
uspto-grants-2011_09
Patent number
US08026257B2

Reaction notes

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