Dibromomethane → HCID 21250649, compound

HRID 1531811Notes

Reaction equation

HRID 1531811 reaction equation
BrCBr.Cl[Si](C)(C)C.I[CH:10]1[CH2:13][CH2:12][N:11]1[C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15].I[C:22]1[CH:29]=[CH:28][C:25]([CH:26]=[O:27])=[CH:24][CH:23]=1.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>CN(C=O)C.[Zn].[O-]S([O-])(=O)=O.[Zn+2]>[CH:26]([C:25]1[CH:28]=[CH:29][C:22]([CH:13]2[CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10]2)=[CH:23][CH:24]=1)=[O:27]

Participants

9

Reactant 5

HCID 3024DibromomethaneHCID 6397ChlorotrimethylsilaneHCID 966574-IodobenzaldehydeHCID 521585Tris(furan-2-yl)phosphaneHCID 21250577HCID 21250577, compound

Product 1

HCID 21250649HCID 21250649, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalyst2×HCID 24424Zinc SulfateCatalystHCID 6228DimethylformamideSolvent4×

Conditions

Temperature
70 °C

Procedure

Zinc dust (253 mg) was stirred under nitrogen overnight. To this was added DMF (5 ml) and dibromomethane (55 mg) dissolved in DMF (1 ml) and the mixture warmed to ˜70° C. The reaction mixture was cooled to room temperature and chlorotrimethylsilane (32 mg) in DMF (1 ml) added and stirred at room temperature for 15 minutes. To this was added 2-iodo-N-Boc-azetidine (Billotte, S., Synlett, 1998, 379-380) (1.04 g) in DMF (5 ml). The reaction mixture warmed to 40° C. and the mixture sonicated for 30 minutes during which time the zinc powder dissolved to leave a hazy solution. To the solution of zincate was added 4-iodobenzaldehyde (Preparation 43) (851 mg in 5 ml DMF), tri-2-furylphosphine (35 mg in 1 ml DMF) and Pd(dbq)2 (42 ml in 1 ml DMF). The resulting mixture was heated at 60-70° C. for 4 hours, cooled to room temperature and partitioned between ammonium chloride solution and diethyl ether, and the aqueous layer was extracted with diethyl ether (3×). The combined organic extracts were dried (Na2SO4), evaporated in vacuo and purified over silica (pentane:ethyl acetate; 4:1) to afford the title compound as a mobile oil, 626 mg.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. temperatureThe reaction mixture warmed to 40° C.
  3. dissolutiondissolved
  4. customto leave a hazy solution
  5. temperatureThe resulting mixture was heated at 60-70° C. for 4 hours
  6. temperaturecooled to room temperature
  7. custompartitioned between ammonium chloride solution and diethyl ether
  8. extractionthe aqueous layer was extracted with diethyl ether (3×)
  9. dry with materialThe combined organic extracts were dried (Na2SO4)
  10. customevaporated in vacuo
  11. custompurified over silica (pentane:ethyl acetate; 4:1)

Sources & evidence

ORD record
ord-323e4c0949d04e15b5122a2b3f798784
Source dataset
uspto-grants-2001_03
Patent number
US06200978B1

Reaction notes

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