Potassium bis(trimethylsilyl)amide → ethyl 4-methylene-7,8-dihydro-4H-thieno[2,3-d]azepine-6(5H)-carboxylate

HRID 1365611Notes

Reaction equation

HRID 1365611 reaction equation
[CH3:1][Si]([N-][Si](C)(C)C)(C)C.[K+].[CH2:11]([O:13][C:14]([N:16]1[CH2:22][C:21](=O)[C:20]2[CH:24]=[CH:25][S:26][C:19]=2[CH2:18][CH2:17]1)=[O:15])[CH3:12]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH2:11]([O:13][C:14]([N:16]1[CH2:22][C:21](=[CH2:1])[C:20]2[CH:24]=[CH:25][S:26][C:19]=2[CH2:18][CH2:17]1)=[O:15])[CH3:12]

Participants

5

Reactant 2

HCID 3251421Potassium bis(trimethylsilyl)amideHCID 574239834-Oxo-4,5,7,8-tetrahydro-thieno[2,3-d]azepine-6-carboxylic acid ethyl ester

Product 1

HCID 58293774ethyl 4-methylene-7,8-dihydro-4H-thieno[2,3-d]azepine-6(5H)-carboxylateYield 87.6%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Methyl triphenylphosphonium bromide (6.3 g, 17.6 mmol) was dissolved in 150 mL THF and cooled to 0° C. KHMDS (3.2 g, 16.2 mmol) was added portionwise and the reaction was stirred for ½ hour. The product of Example 1, step (c) (3.0 g, 12.5 mmol) was added as a solution in 25 μL THF. The reaction was warmed to room temperature and stirred for 1 hour. The mixture was concentrated and the title product was purified by silica gel chromatography (0% to 40% EtOAc in hexanes) to give 2.6 g of the sub-title compound.

Workup

  1. temperatureThe reaction was warmed to room temperature
  2. stirringstirred for 1 hour
  3. concentrationThe mixture was concentrated
  4. customthe title product was purified by silica gel chromatography (0% to 40% EtOAc in hexanes)

Sources & evidence

ORD record
ord-732b2b189f3848a0a4f877c66026f5e7
Source dataset
uspto-grants-2011_02
Patent number
US07893051B2

Reaction notes

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