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(R)-2-allyl-4-(tert-butyldimethylsilyloxy)cyclopent-2-enone → (2R,3R,4R)-2-allyl-4-(tert-butyldimethylsilyloxy)-3-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)cyclopentanone

HRID 517379
Notes
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Reaction equation

HRID 517379 reaction equation
[CH2:1]([Si:3]([CH2:35][CH3:36])([CH2:33][CH3:34])[O:4][C@H:5](/[CH:18]=[CH:19]/[Sn](CCCC)(CCCC)CCCC)[CH2:6][O:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([F:17])([F:16])[F:15])[CH:9]=1)[CH3:2].C([Li])CCC.[Cu](C#N)C#N.C[Li].[CH2:49]([C:52]1[C:53](=[O:65])[CH2:54][C@@H:55]([O:57][Si:58]([C:61]([CH3:64])([CH3:63])[CH3:62])([CH3:60])[CH3:59])[CH:56]=1)[CH:50]=[CH2:51].[NH4+].[Cl-].[NH4+].[OH-]>O1CCCC1>[CH2:49]([C@@H:52]1[C@@H:56](/[CH:19]=[CH:18]/[C@@H:5]([O:4][Si:3]([CH2:35][CH3:36])([CH2:1][CH3:2])[CH2:33][CH3:34])[CH2:6][O:7][C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([F:17])([F:16])[F:15])[CH:9]=2)[C@H:55]([O:57][Si:58]([C:61]([CH3:64])([CH3:63])[CH3:62])([CH3:59])[CH3:60])[CH2:54][C:53]1=[O:65])[CH:50]=[CH2:51]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 6

HCID 14189023(R)-2-allyl-4-(tert-butyldimethylsilyloxy)cyclopent-2-enoneHCID 21863491Ammonium chloride ammonium hydroxideHCID 67428430(R,E)-triethyl(4-(tributylstannyl)-1-(3-(trifluoromethyl)phenoxy)but-3-en-2-yloxy)silaneHCID 178418260HCID 178418260, compoundHCID 178418339ButyllithiumHCID 178418348
HCID 178418348, compound

Product 1

HCID 131733344(2R,3R,4R)-2-allyl-4-(tert-butyldimethylsilyloxy)-3-((R,E)-3-(triethylsilyloxy)-4-(3-(trifluoromethyl)phenoxy)but-1-enyl)cyclopentanoneYield 37.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A 100 ml three-necked flask was flame dried and allowed to be cooled under nitrogen. (R,E)-triethyl(4-(tributylstannyl)-1-(3-(trifluoromethyl)phenoxy)but-3-en-2-yloxy)silane (15.11 g, 23.8 mmol) and 20 ml tetrahydrofuran were added to the reaction flask, followed by dropwise addition of n-butyl lithium (14.9 ml, 1.6 M in hexane) at −70° C. A suspension solution of copper cyanide (2.13 g, 23.8 mmol) in 20 ml tetrahydrofuran was cooled to −20° C., followed by dropwise addition of methyl lithium (11.9 ml, 2 M in ether). The homogenous organo-metallic solution was cooled and added into the reaction flask while stirring for 60 minutes. Then, a solution of (R)-2-allyl-4-(tert-butyldimethylsilyloxy)cyclopent-2-enone (3 g, 11.9 mmol) in 20 ml tetrahydrofuran at −70° C. was added to the reaction mixture for 10 minutes. After being stirred for another 20 minutes, the reaction mixture was poured into a mixture of 9/1 (v/v) saturated aqueous NH4Cl/NH4OH solution to be phase separated. The aqueous layer was extracted with ethyl acetate. The organic layers were combined and dried over magnesium sulfate. The solid was filtered off and organic solvent was evaporated off under vacuum. The crude product was purified by chromatography and then concentrated under reduced pressure to provide 2.68 g of the title compound (37.7% yield).

Workup

  1. temperatureA 100 ml three-necked flask was flame
  2. customdried
  3. temperatureto be cooled under nitrogen
  4. additionadded into the reaction flask
  5. stirringAfter being stirred for another 20 minutes
  6. customseparated
  7. extractionThe aqueous layer was extracted with ethyl acetate
  8. dry with materialdried over magnesium sulfate
  9. filtrationThe solid was filtered off
  10. customorganic solvent was evaporated off under vacuum
  11. customThe crude product was purified by chromatography
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b462cf8886a34f55834ff7be2617ada9
Source dataset
uspto-grants-2015_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09115109B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes