Chlorotrimethylsilane → HCID 68160088, compound

HRID 1468768Notes

Reaction equation

HRID 1468768 reaction equation
Cl[Si](C)(C)C.BrCCBr.I[CH:11]1[CH2:20][CH2:19][C:14]2([O:18][CH2:17][CH2:16][O:15]2)[CH2:13][CH2:12]1.Br[C:22]1[CH:36]=[CH:35][C:25]([CH2:26][O:27][Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])=[CH:24][CH:23]=1>CN(C)C(=O)C.[Zn].O>[C:31]([Si:28]([O:27][CH2:26][C:25]1[CH:24]=[CH:23][C:22]([CH:11]2[CH2:20][CH2:19][C:14]3([O:18][CH2:17][CH2:16][O:15]3)[CH2:13][CH2:12]2)=[CH:36][CH:35]=1)([CH3:30])[CH3:29])([CH3:34])([CH3:32])[CH3:33]

Participants

8

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 108595834-Bromobenzyloxy-tert-butyldimethylsilaneHCID 110218798-Iodo-1,4-dioxaspiro[4.5]decane

Product 1

HCID 68160088HCID 68160088, compoundYield 74.2%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 962WaterSolventHCID 31374DimethylacetamideSolvent3×

Procedure

To a mixture of zinc powder (5.52 g, 84.5 mmol) and Celite (1.1 g) in N,N-dimethylacetamide (14 ml) was added dropwise chlorotrimethylsilane (0.930 ml, 7.33 mmol) in 1,2-dibromoethane (0.665 ml, 7.54 mmol) at 0° C. under nitrogen atmosphere. The mixture was warmed to room temperature, and stirred for 20 minutes. 8-Iodo-1,4-dioxa-spiro[4.5]decane (18.1 g, 67.6 mmol) in N,N-dimethylacetamide (34 ml) was then added dropwise at 0° C. The mixture was stirred for 30 minutes at room temperature, and the supernatant solution was added dropwise to the mixture of (4-bromobenzyloxy) (tert-butyl)dimethylsilane (15.7 g, 52.0 mmol), copper iodide(I) (792 mg, 4.16 mmol) and [1,1′-bis(diphenylphosphino) ferrocene]dichloropalladium(II)dichloromethane complex (1.70 g, 2.08 mmol) in N,N-dimethylacetamide (74 ml) at room temperature under nitrogen atmosphere. The mixture was stirred at 80° C. for 5 hours. The mixture was poured into the cold water, and extracted with ethyl acetate. The organic layer was washed with water (three times), dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate=92/8) to afford tert-butyl-[4-(1,4-dioxa-spiro[4.5]dec-8-yl)benzyloxy]dimethylsilane as a pale yellow oil (14.0 g, 38.6 mmol, 74%).

Workup

  1. stirringThe mixture was stirred for 30 minutes at room temperature
  2. stirringThe mixture was stirred at 80° C. for 5 hours
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with water (three times)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel column chromatography (eluent; hexane/ethyl acetate=92/8)

Sources & evidence

ORD record
ord-09b4839be53d4bdfad95a54e5de44b79
Source dataset
uspto-grants-2015_04
Patent number
US09006232B2

Reaction notes

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