1,4-Bis(diphenylphosphino)butane → 1,1-Dimethylethyl cyclopropyl{[2,3-dichloro-5-(2-hydroxyethyl)phenyl]methyl}carbamate

HRID 337552

反応式

HRID 337552 の反応式
[CH:1]1([N:4]([CH2:12][C:13]2[CH:18]=[C:17]([CH:19]=[CH2:20])[CH:16]=[C:15]([Cl:21])[C:14]=2[Cl:22])[C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8])[CH2:3][CH2:2]1.C1C=CC(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC1(C)C(C)(C)OB[O:55]1.B(O[O-])=O.[Na+]>C1COCC1>[CH:1]1([N:4]([CH2:12][C:13]2[CH:18]=[C:17]([CH2:19][CH2:20][OH:55])[CH:16]=[C:15]([Cl:21])[C:14]=2[Cl:22])[C:5](=[O:11])[O:6][C:7]([CH3:8])([CH3:9])[CH3:10])[CH2:3][CH2:2]1

参加物

6

反応物 4

HCID 821241,4-Bis(diphenylphosphino)butaneHCID 517072Sodium PerborateHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 668954141,1-Dimethylethyl cyclopropyl[(2,3-dichloro-5-ethenylphenyl)methyl]carbamate

生成物 1

HCID 668971121,1-Dimethylethyl cyclopropyl{[2,3-dichloro-5-(2-hydroxyethyl)phenyl]methyl}carbamate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

1,1-Dimethylethyl cyclopropyl[(2,3-dichloro-5-ethenylphenyl)methyl]carbamate (1 eq.) from the previous step, [Ir(COD)Cl]2 (0.025 eq.) and DPPB (0.05 eq.) were combined in THF (0.11 M). To this solution was then added 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.3 eq.) and the resulting red solution was stirred at RT for 12 h. Finally, sodium perborate (0.1 M aqueous solution, 1 eq.) was added and the now black biphasic solution was vigorously stirred at RT for another 12 h. The aqueous layer was separated and back-extracted with ether. The combined organic extracts were then washed further with 1 N aq. NaOH, water and brine. This was then dried over Na2SO4, filtered and the filtrate concentrated in vacuo to afford a pale yellow oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→3:7 (v/v) EtOAc:Hex) afforded the title compound as a colorless oil.

後処理

  1. customThe aqueous layer was separated
  2. extractionback-extracted with ether
  3. washThe combined organic extracts were then washed further with 1 N aq. NaOH, water and brine
  4. dry with materialThis was then dried over Na2SO4
  5. filtrationfiltered
  6. concentrationthe filtrate concentrated in vacuo
  7. customto afford a pale yellow oil
  8. customPurification of the crude product
  9. customthus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→3:7 (v/v) EtOAc:Hex)

出典と根拠

ORDレコード
ord-b146069054414e8eb218ee37d816b6d7
出典データセット
uspto-grants-2014_11
特許番号
US08889714B2

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