Tetrahydrofuran → HCID 131728794, compound

HRID 628005Notes

Reaction equation

HRID 628005 reaction equation
[Si:1]([O:8][CH2:9][C:10]1[CH:20]=[N:19][C:18]2[C:17]3[S:21][C:22](Br)=[CH:23][C:16]=3[CH2:15][CH2:14][O:13][C:12]=2[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].O1CCCC1.C([Li])C[CH2:32][CH3:33].Cl[C:36]([O:38]CC)=[O:37]>CCCCCC>[Si:1]([O:8][CH2:9][C:10]1[C:20]([C:36]([OH:38])=[O:37])=[N:19][C:18]2[C:17]3[S:21][C:22]([CH2:32][CH3:33])=[CH:23][C:16]=3[CH2:15][CH2:14][O:13][C:12]=2[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 10928Ethyl chloroformateHCID 57900148HCID 57900148, compoundHCID 178418339Butyllithium

Product 1

HCID 131728794HCID 131728794, compoundYield 36%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 3-tert-butyldimethylsilyloxymethyl-9-bromo-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine (0.0500 g, 0.117 mmol;) in tetrahydrofuran (1.78 mL, 22.0 mmol) was added 1.60 M of n-butyllithium in hexane (0.0806 mL) dropwise at −78° C. The reaction mixture was stirred at −78° C. for 1 h. Ethyl chloroformate (0.0336 mL, 0.352 mmol;) was added to the mixture at −78° C. then let stirred 2 h. The reaction mixture was quenched with sat. NaHCO3 then extracted EtOAc (2×). The combined organic layers was dried Na2SO4, concentrated. The crude product was purified by flash chromatography (0-50% EtOAc/Hex) (eluted 15%) to give 3-tert-butyldimethylsilyloxymethyl-9-ethylcarboxy-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine (36% yield). MS: (ESI+) 420.1

Workup

  1. stirringthen let stirred 2 h
  2. customThe reaction mixture was quenched with sat. NaHCO3
  3. concentrationconcentrated
  4. customThe crude product was purified by flash chromatography (0-50% EtOAc/Hex) (eluted 15%)

Sources & evidence

ORD record
ord-c3ffebd9b653420784c7a135bc54a350
Source dataset
uspto-grants-2016_04
Patent number
US09309265B2

Reaction notes

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