Chlorotrimethylsilane → HCID 22097562, compound

HRID 1458900Notes

Reaction equation

HRID 1458900 reaction equation
[C:1]1([Mg]Br)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:9]([C:12]12[CH2:19][CH2:18][N:15]([CH2:16][CH2:17]1)[C:14](=[CH:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:13]2=[O:27])[CH:10]=[CH2:11].C[Si](Cl)(C)C.CN(P(N(C)C)(N(C)C)=O)C>[Cu].C1(C)C=CC=CC=1>[CH2:9]([C:12]12[CH2:17][CH2:16][N:15]([CH2:18][CH2:19]1)[CH:14]([CH:20]([C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:13]2=[O:27])[CH:10]=[CH2:11]

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 12679HexamethylphosphoramideHCID 54548584HCID 54548584, compoundHCID 178418255HCID 178418255, compound

Product 1

HCID 22097562HCID 22097562, compoundYield 68%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
0 °C

Procedure

Copper(I) bromide dimethyl sulfide complex (1.06 g, 5.16 mmol) and 100 ml of toluene were placed in a reaction vessel, which was immersed into an dry-ice acetone bath. Phenylmagnesium bromide (3.0M in ether, 42 ml, 126 mmol) was slowly added to the copper catalyst keeping the inner temperature below -60° C. To this yellow-white suspension was added a solution prepared from 4-allyl-2-benzylidene-1-azabicyclo-[2.2.2]octane-3-one (25.9 g, 103 mmol), trimethylsilyl chloride (31.4 ml, 247 mmol), HMPA (43 ml, 247 mmol) and toluene (120 ml) keeping below -60° C. After addition was completed, the reaction mixture was warmed up to 0° C. The reaction was quenched with 14.5 ml of acetic acid at -60° C. Water was added to the reaction mixture, which was neutralized with Na2CO3 (pH=6.5). The resulting solution was worked-up by an ordinal procedure (extraction with ether at pH=6.5, and then at pH=8.0, washing with brine, drying over Na2SO4, concentration by evaporation) to provide a crude product, which was triturated with ether to afford 4-allyl-2-diphenylmethyl-1-azabicyclo[2.2.2]octane-3-one, 58 (23.04 g, 68%).

Workup

  1. customwhich was immersed into an dry-ice acetone bath
  2. customthe inner temperature below -60° C
  3. additionTo this yellow-white suspension was added a solution
  4. customkeeping below -60° C
  5. additionAfter addition
  6. customThe reaction was quenched with 14.5 ml of acetic acid at -60° C
  7. additionWater was added to the reaction mixture, which
  8. extractionextraction with ether at pH=6.5
  9. washat pH=8.0, washing with brine
  10. dry with materialdrying over Na2SO4, concentration by evaporation)
  11. customto provide a crude product, which
  12. customwas triturated with ether

Sources & evidence

ORD record
ord-f88726ff0ff94a0dbc261716fe10cb5f
Source dataset
uspto-grants-1998_12
Patent number
US05852038

Reaction notes

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