4,5-Diphenyloxazole → (R)-2-(4,5-diphenyloxazol-2-yl)-1-trimethylsilyloxy-1-[3-(tertbutyldiphenylsiloxy)benzyl]-2-cyclohexene

HRID 379314Notes

Reaction equation

HRID 379314 reaction equation
[C:1]1([C:7]2[N:8]=[CH:9][O:10][C:11]=2[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li]CCCC.[C:23]([Si:27]([C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1)([C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)[O:28][C:29]1[CH:30]=[C:31]([CH:45]=[CH:46][CH:47]=1)[CH2:32][C@:33]1([O:40][Si:41]([CH3:44])([CH3:43])[CH3:42])[CH2:38][CH2:37][CH2:36][CH2:35][C:34]1=O)([CH3:26])([CH3:25])[CH3:24].[OH-].COC(NS([N+](CC)(CC)CC)(=O)=O)=O>C1COCC1.C1(C)C=CC=CC=1>[C:1]1([C:7]2[N:8]=[C:9]([C:34]3[C@:33]([O:40][Si:41]([CH3:44])([CH3:43])[CH3:42])([CH2:32][C:31]4[CH:45]=[CH:46][CH:47]=[C:29]([O:28][Si:27]([C:23]([CH3:26])([CH3:24])[CH3:25])([C:54]5[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=5)[C:48]5[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=5)[CH:30]=4)[CH2:38][CH2:37][CH2:36][CH:35]=3)[O:10][C:11]=2[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 6134984,5-DiphenyloxazoleHCID 11032497(Methoxycarbonylsulfamoyl)triethylammonium hydroxideHCID 86757468(R)-1-[3-(tertbutyldiphenyl-silyloxy)benzyl]-1-trimethylsilyoxy-2-cyclohexanoneHCID 178418339Butyllithium

Product 1

HCID 15550206(R)-2-(4,5-diphenyloxazol-2-yl)-1-trimethylsilyloxy-1-[3-(tertbutyldiphenylsiloxy)benzyl]-2-cyclohexeneYield 96.4%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of (4,5-diphenyl)oxazole (17 g) in THF (100 ml) was added n-BuLi (57 ml, 1.6N-solution in hexane) at −78° C. After stirring for 30 minutes, a solution of (R)-1-[3-(tertbutyldiphenyl-silyloxy)benzyl]-1-trimethylsilyoxy-2-cyclohexanone (27 g) in THF (50 ml) was added to the above mixture at the same temperature. After stirring for 1 hour, the reaction mixture was partitioned between EtOAc and water. The organic layer was washed with 1N-HCl solution and brine. The organic solvent was evaporated in vacuo to give a residue. The residue was dissolved in toluene (100 ml) and then added with (methoxycarbonylsulfamoyl)triethyl-ammonium hydroxide, inner salt(20.4 g) at room temperature. After refluxing under stirring for 5 hours, the reaction mixture was evaporated in vacuo. The residue was purified by chromatography on silica gel to give (R)-2-(4,5-diphenyloxazol-2-yl)-1-trimethylsilyloxy-1-[3-(tertbutyldiphenylsiloxy)benzyl]-2-cyclohexene (36 g).

Workup

  1. stirringAfter stirring for 1 hour
  2. customthe reaction mixture was partitioned between EtOAc and water
  3. washThe organic layer was washed with 1N-HCl solution and brine
  4. customThe organic solvent was evaporated in vacuo
  5. customto give a residue
  6. temperatureAfter refluxing
  7. stirringunder stirring for 5 hours
  8. customthe reaction mixture was evaporated in vacuo
  9. customThe residue was purified by chromatography on silica gel

Sources & evidence

ORD record
ord-b6ef327c3f1f48879cd6580a73ab4eb4
Source dataset
uspto-grants-2001_10
Patent number
US06297267B1

Reaction notes

Loading…