HCID 71268595, compound → HCID 71268562, compound

HRID 39609Notes

Reaction equation

HRID 39609 reaction equation
[C:1]([Si:5]([O:8][C@@H:9]([CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH2:10][CH2:11]I)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C([Li])(C)(C)C.[Cu](C#N)C#N.C[Li].[CH2:30]([O:37][C:38]1[CH:39]=[C:40]([CH:56]=[CH:57][CH:58]=1)[CH2:41][C:42]1[C:43](=[O:55])[CH2:44][C@@H:45]([O:47][Si:48]([C:51]([CH3:54])([CH3:53])[CH3:52])([CH3:50])[CH3:49])[CH:46]=1)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1>CCOCC>[CH2:30]([O:37][C:38]1[CH:39]=[C:40]([CH:56]=[CH:57][CH:58]=1)[CH2:41][C@@H:42]1[C@@H:46]([CH2:11][CH2:10][C@@H:9]([O:8][Si:5]([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:7])[CH3:6])[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[C@H:45]([O:47][Si:48]([C:51]([CH3:52])([CH3:53])[CH3:54])([CH3:49])[CH3:50])[CH2:44][C:43]1=[O:55])[C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1

Participants

7

Reactant 5

HCID 71268595HCID 71268595, compoundHCID 89413771(S)-tert-butyl(1-iodooctan-3-yloxy)dimethylsilaneHCID 178418260HCID 178418260, compoundHCID 178418306HCID 178418306, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 71268562HCID 71268562, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

A 25 ml two-necked flask was flame dried and allowed to be cooled. (S)-tert-butyl(1-iodooctan-3-yloxy)dimethylsilane (1.18 g, 3.2 mmol) and 11.8 L ether were added to the reaction flask, followed by dropwise addition of tert-butyl-lithium (3.75 ml, 1.7M in pentane) at −70° C. A homogenous solution of copper cyanide (0.29 g, 3.2 mmol) and methyllithium (1.6 ml, 2M in ether) in 5.8 ml ether was cooled from room temperature to −70° C. and added to the reaction flask while stirring for 30 minutes. Then, a solution of (R)-2-(3-(benzyloxy)benzyl)-4-(tert-butyldimethylsilyloxy)cyclopent-2-enone (0.65 g, 1.6 mmol) in 6.5 ml ether at −70° C. was added to the reaction mixture for 30 minutes. The reaction was quenched with 40 ml saturated ammonium chloride (aq) containing 0.4 ml ammonium hydroxide. The reaction mixture was phase separated and the aqueous layer was extracted with ethyl acetate. The organic layers were combined and dried over anhydrous magnesium sulfate. The solid was filtered off. The solvent was evaporated off under vacuum. The crude product was purified by chromatography on silica gel using a mixture of hexane and ethyl acetate as a gradient eluent. Yield of the titled compound was 1.1 g (85%).

Workup

  1. temperatureA 25 ml two-necked flask was flame
  2. customdried
  3. temperatureto be cooled
  4. additionadded to the reaction flask
  5. customThe reaction was quenched with 40 ml saturated ammonium chloride (aq)
  6. additioncontaining 0.4 ml ammonium hydroxide
  7. customseparated
  8. extractionthe aqueous layer was extracted with ethyl acetate
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationThe solid was filtered off
  11. customThe solvent was evaporated off under vacuum
  12. customThe crude product was purified by chromatography on silica gel using
  13. additiona mixture of hexane and ethyl acetate as a gradient eluent

Sources & evidence

ORD record
ord-07fccfd5bd4c4dcc93af0ec0e0dd9b1c
Source dataset
uspto-grants-2013_09
Patent number
US08524939B2

Reaction notes

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