Chlorotrimethylsilane → HCID 59633969, compound

HRID 1615062Notes

Reaction equation

HRID 1615062 reaction equation
[Cl-].[Li+].BrC(Br)C.Cl[Si](C)(C)C.[C:12]([N:19]1[CH2:22][CH:21](I)[CH2:20]1)([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13].[CH2:24]([C:26]1[CH:42]=[CH:41][C:29]([CH2:30][O:31][C:32]2[CH:37]=[CH:36][C:35](I)=[CH:34][C:33]=2[O:39][CH3:40])=[CH:28][CH:27]=1)[CH3:25].[NH4+].[Cl-]>O1CCCC1.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Zn]>[CH2:24]([C:26]1[CH:42]=[CH:41][C:29]([CH2:30][O:31][C:32]2[CH:37]=[CH:36][C:35]([CH:21]3[CH2:22][N:19]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:20]3)=[CH:34][C:33]=2[O:39][CH3:40])=[CH:28][CH:27]=1)[CH3:25]

Participants

10

Reactant 6

HCID 6397ChlorotrimethylsilaneHCID 112011,1-DibromoethaneHCID 25517Ammonium ChlorideHCID 433294Lithium ChlorideHCID 11000522Tert-butyl 3-iodoazetidine-1-carboxylateHCID 59633913HCID 59633913, compound2×

Product 1

HCID 59633969HCID 59633969, compoundYield 52%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×HCID 178419050HCID 178419050, compoundSolvent

Conditions

Temperature
70 °C

Procedure

To a suspension of zinc (20.7 g) and lithium chloride (10 g) in THF (120 mL) were added dibromoethane (2 mL) and chlorotrimethylsilane (3 mL) at 70° C. under argon atmosphere. The mixture was stirred at 70° C. for 10 min. A solution of 1-Boc-3-iodoazetidine (67 g) in THF (120 mL) was added dropwise to the mixture at RT. The reaction mixture was stirred for 1 hr. To the mixture were added a solution of 1-(4-ethylbenzyloxy)-4-iodo-2-methoxybenzene (58.1 g) prepared in (1) in THF (120 mL) and bis(triphenylphosphine)palladium (II) dichloride (0.49 g). The reaction mixture was stirred at RT for 3 hr. Saturated aqueous NH4Cl was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was dried over MgSO4. The solvent was removed under reduced pressure. The residue was purified by silica gel chromatography (Developing solvent: hexane/ethyl acetate=4/1) to give the title compound (32.4 g, 52%).

Workup

  1. stirringThe reaction mixture was stirred for 1 hr
  2. stirringThe reaction mixture was stirred at RT for 3 hr
  3. extractionthe mixture was extracted with ethyl acetate
  4. dry with materialThe organic layer was dried over MgSO4
  5. customThe solvent was removed under reduced pressure
  6. customThe residue was purified by silica gel chromatography (Developing solvent: hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-9dc5629361fd43a19e84ffbb900a68c0
Source dataset
uspto-grants-2014_07
Patent number
US08765739B2

Reaction notes

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