Tetrahydrofuran → HCID 69371688, compound

HRID 724377Notes

Reaction equation

HRID 724377 reaction equation
[Li][C:2]([CH3:5])([CH3:4])[CH3:3].I[C:7]1[C:15]2[C:10](=[CH:11][C:12]([C:16]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH2:17])=[CH:13][CH:14]=2)[N:9]([CH2:24][O:25][CH2:26][CH2:27][Si:28]([CH3:31])([CH3:30])[CH3:29])[N:8]=1.[C:32](=O)(O)[O-].[Na+].[CH2:37]1[CH2:41]OC[CH2:38]1>[Cl-].[Zn+2].[Cl-].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>[C:18]1([C:16]([C:12]2[CH:11]=[C:10]3[C:15]([C:7]([CH:32]=[CH:3][C:2]4[CH:5]=[CH:41][CH:37]=[CH:38][CH:4]=4)=[N:8][N:9]3[CH2:24][O:25][CH2:26][CH2:27][Si:28]([CH3:31])([CH3:30])[CH3:29])=[CH:14][CH:13]=2)=[CH2:17])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 4

HCID 8028TetrahydrofuranHCID 516892Sodium BicarbonateHCID 21877301HCID 21877301, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 69371688HCID 69371688, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
-42 °C

Procedure

E-2-Bromostyrene (23 μL, 0.174 mmol, 2.5 equiv) was dissolved in THF (1.0 mL) and was cooled to −78° C. t-BuLi (205 μL, 0.348 mmol, 5.00 equiv) was added and the mixture was warmed to −42° C. for 7 min to give a deep red mixture. The solution was added to freshly dried zinc chloride (29 mg, 0.209 mmol, 3.00 equiv) via cannula and the mix was allowed to warm to 23° C. with stirring for 20 min. This solution was added to a neat mixture of 3-Iodo-6-(1-phenyl-vinyl)-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazole (33.1 mg, 0.0696 mmol, 1.0 equiv) and Pd(PPh3)4 (4 mg, 0.0035 mmol, 0.05 equiv) at 23° C. via cannula. This solution was allowed to stir for 15 min and was treated with saturated sodium bicarbonate and extracted with ethyl acetate. The organic material was dried over sodium sulfate, decanted and concentrated. Purification by silica gel chromatography using two columns (5:95 ethyl acetate-hexane; 12 mL silica: and 1:99 ethyl acetate-benzene; 12 mL silica) gave 6-(1-Phenyl-vinyl)-3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazole (16.2 mg, 51%): Rf sm 0.38, p 0.29 (ethyl acetate-hexane 1:9); 1H NMR (300 MHz, CDCl3) δ 7.98 (d, 1H, J=8.4 Hz), 7.62–7.22 (m, 14H), 5.71 (s, 2H), 5.57 (s, 2H), 3.60 (t, 2H, J=8.2 Hz), 0.90 (t, 2H, J=8.2 Hz), −0.08 (s, 9H); HRMS (FAB) [m+H]/z Calc'd 453.2362. Found 453.2354.

Workup

  1. additionwas added
  2. customto give a deep red mixture
  3. temperatureto warm to 23° C.
  4. stirringto stir for 15 min
  5. extractionextracted with ethyl acetate
  6. dry with materialThe organic material was dried over sodium sulfate
  7. customdecanted
  8. concentrationconcentrated
  9. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-7b448a10035b4bc5b43ddafbf94ae584
Source dataset
uspto-grants-2006_11
Patent number
US07141587B2

Reaction notes

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