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Dimethylformamide → (1S)-1-(2-{[tert-Butyl(diphenyl)silyl]oxy}ethyl)-3,4-dihydro-1H-2-benzopyran-6-carbaldehyde

HRID 2056758
Notes
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Reaction equation

HRID 2056758 reaction equation
[Si:1]([O:18][CH2:19][CH2:20][C@H:21]1[C:26]2[CH:27]=[CH:28][C:29](Br)=[CH:30][C:25]=2[CH2:24][CH2:23][O:22]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.CN(C)[CH:39]=[O:40]>C1COCC1>[Si:1]([O:18][CH2:19][CH2:20][C@H:21]1[C:26]2[CH:27]=[CH:28][C:29]([CH:39]=[O:40])=[CH:30][C:25]=2[CH2:24][CH2:23][O:22]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 693073122-((1S)-6-Bromo-3,4-dihydro-1H-2-benzopyran-1-yl)ethyl tert-butyl(diphenyl)silyl etherHCID 178418339Butyllithium

Product 1

HCID 86596016(1S)-1-(2-{[tert-Butyl(diphenyl)silyl]oxy}ethyl)-3,4-dihydro-1H-2-benzopyran-6-carbaldehyde

Reagents, catalysts & solvents 1

HCID 8028
Tetrahydrofuran
Solvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of 2-((1S)-6-bromo-3,4-dihydro-1H-2-benzopyran-1-yl)ethyl tert-butyl(diphenyl)silyl ether (2.5 g, 5.05 mmol) in dry THF (60 mL), cooled to −78° C. under nitrogen, was slowly added n-butyllithium (2.5M in THF) (5.4 mL, 13.5 mmol). After 30 min stirring at −78° C., dry dimethylformamide (3.5 mL, 45 mmol) was added and the reaction allowed to warm to room temperature overnight. The reaction was quenched by addition of water and extracted into ethyl acetate. The combined organic extracts were washed with brine, dried (MgSO4), filtered and evaporated in vacuo. The resultant yellow oil was purified by flash chromatography on silica, eluting with ethyl acetate/hexane (0:4 to 1:3), to yield the title compound as a colourless oil.

Workup

  1. temperatureto warm to room temperature overnight
  2. customThe reaction was quenched by addition of water
  3. extractionextracted into ethyl acetate
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customevaporated in vacuo
  8. customThe resultant yellow oil was purified by flash chromatography on silica
  9. washeluting with ethyl acetate/hexane (0:4 to 1:3)

Sources & evidence

ORD record
ord-dee50f8e298343cb8e5f5d6f87e2daca
Source dataset
uspto-grants-2008_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07335660B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes