Phenylboronic Acid → 3-Phenyl-2-thiophenecarboxaldehyde

HRID 530688ノート

反応式

HRID 530688 の反応式
Br[C:2]1[CH:6]=[CH:5][S:4][C:3]=1[CH:7]=[O:8].[C:9]1(B(O)O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>COCCOC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:9]1([C:2]2[CH:6]=[CH:5][S:4][C:3]=2[CH:7]=[O:8])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

参加物

5

反応物 2

HCID 66827Phenylboronic AcidHCID 27970793-Bromothiophene-2-carboxaldehyde

生成物 1

HCID 8188473-Phenyl-2-thiophenecarboxaldehyde収率 34%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
80 °C

実験手順

3-Bromothiophene-2-carbaldehyde (3 g, 1.67 ml, 14.8 mmol, CAS RN 930-96-1) was dissolved in DME (180 mL) and the resulting solution was evacuated and purged with argon three times. Pd(Ph3P)4 (512 mg, 443 μmol) was added, the reaction flask purged again with argon and stirring was continued at RT for 15 min. Then 2M aqueous Na2CO3 solution was added (14.8 mL, 29.5 mmol) followed by phenylboronic acid (1.98 g, 16.2 mmol). Again the reaction flask was purged with argon and the reaction mixture was heated to 80° C. and stirred for 6.5 h. After evaporation of the solvent, the residue was taken up in Et2O and H2O and the layers were separated. The organic layer was dried over Na2SO4, filtered and evaporated. The crude residue was suspended in CH2Cl2 and n-heptane and the solid was filtered off. The filtrate was evaporated and the crude product purified by flash chromatography on silica gel (gradient EtOAc/n-heptane, 0% to 10%). The product-containing fractions were pooled and further purified by preparative HPLC to give the title compound as a yellow oil (0.939 g, 34%). MS (ESI): m/z=189.2 [M+H]+.

後処理

  1. customthe resulting solution was evacuated
  2. custompurged with argon three times
  3. customthe reaction flask purged again with argon
  4. additionThen 2M aqueous Na2CO3 solution was added (14.8 mL, 29.5 mmol)
  5. customAgain the reaction flask was purged with argon
  6. stirringstirred for 6.5 h
  7. customAfter evaporation of the solvent
  8. customH2O and the layers were separated
  9. dry with materialThe organic layer was dried over Na2SO4
  10. filtrationfiltered
  11. customevaporated
  12. filtrationn-heptane and the solid was filtered off
  13. customThe filtrate was evaporated
  14. customthe crude product purified by flash chromatography on silica gel (gradient EtOAc/n-heptane, 0% to 10%)
  15. customfurther purified by preparative HPLC

出典と根拠

ORDレコード
ord-c564547cc4ed48dbb4d34a3ef352889a
出典データセット
uspto-grants-2016_05
特許番号
US09353102B2

反応ノート

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