Sodium Iodide → 4-trimethylsilanyloxy-7,8-dihydro-6H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

HRID 481073Notes

Reaction equation

HRID 481073 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:22](=[O:23])[CH2:21][CH2:20][CH2:19][CH2:18][C:8]=2[N:9]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH:10]=1)=[O:5])[CH3:2].[Na+].[I-].C(N(CC)CC)C.[CH3:33][Si:34](Cl)([CH3:36])[CH3:35]>CC#N>[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:22]([O:23][Si:34]([CH3:36])([CH3:35])[CH3:33])=[CH:21][CH2:20][CH2:19][CH2:18][C:8]=2[N:9]([C:11]([O:13][C:14]([CH3:17])([CH3:15])[CH3:16])=[O:12])[CH:10]=1)=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 5238Sodium IodideHCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 206056554-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

Product 1

HCID 207622254-trimethylsilanyloxy-7,8-dihydro-6H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl esterYield 100%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester (2.17 g, 6.72 mmol), NaI (1.51 g, 10.07 mmol) and triethylamine (2.80 mL, 20.14 mmol) in CH3CN (30 mL), is added trimethylsilyl chloride (1.27 mL, 10.07 mmol) slowly via syringe. The reaction mixture is stirred at room temperature for 20 h. and then partitioned between 50 mL of ethyl acetate/hexanes (1:1 with a few drops of triethylamine ) and 30 mL of sat. NaHCO3 solution. The layers are separated and the aqueous phase is extracted with ethyl acetate/hexanes (1:1) (3×20 mL). The combined organic layers are washed with brine, dried (Na2SO4) and evaporated to provide 4-trimethylsilanyloxy-7,8-dihydro-6H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester (2.56 g, 100%) as viscous red oil. 1H NMR (400 MHz, CDCl3) δ0.177 (9H, s), 1.308 (3H, t), 1.585 (9H, s), 1.906 (2H, m), 2.016 (2H, m), 2.974 (2H, t), 4.243 (2H, q), 5.353 (1H, t), 7.627 (1H, s). MS (ES+) 395 (M+1).

Workup

  1. custompartitioned between 50 mL of ethyl acetate/hexanes (1:1 with a few drops of triethylamine ) and 30 mL of sat. NaHCO3 solution
  2. customThe layers are separated
  3. extractionthe aqueous phase is extracted with ethyl acetate/hexanes (1:1) (3×20 mL)
  4. washThe combined organic layers are washed with brine
  5. dry with materialdried (Na2SO4)
  6. customevaporated

Sources & evidence

ORD record
ord-e7cfb71f22a84d92b77eeec5c1054a1d
Source dataset
uspto-grants-2003_11
Patent number
US06653471B2

Reaction notes

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