Sodium Chloride → ((1R,4S)-4-Azido-cyclopent-2-enyloxy)-tert-butyl-dimethyl-silane

HRID 402533

反応式

HRID 402533 の反応式
[C:1]([Si:5]([CH3:17])([CH3:16])[O:6][C@@H:7]1[CH2:11][C@H:10](OC(=O)C)[CH:9]=[CH:8]1)([CH3:4])([CH3:3])[CH3:2].O[C@@H]1C[C@H](OC(=O)C)C=C1.[N-:28]=[N+:29]=[N-:30].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl-].[Na+]>O1CCCC1.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[N:28]([C@H:10]1[CH2:11][C@@H:7]([O:6][Si:5]([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:17])[CH3:16])[CH:8]=[CH:9]1)=[N+:29]=[N-:30]

参加物

9

反応物 5

HCID 5234Sodium ChlorideHCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 98554984-Cyclopentene-1,3-diol, 1-acetate, (1R,3S)-rel-HCID 10999690(1S,4R)-4-{[Tert-butyl(dimethyl)silyl]oxy}-2-cyclopenten-1-YL acetate

生成物 1

HCID 86639599((1R,4S)-4-Azido-cyclopent-2-enyloxy)-tert-butyl-dimethyl-silane収率 80.7%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
50 °C

実験手順

The title compound was prepared by combining a solution of 630 mg (2.46 mmol) of acetic acid (1S,4R)-4-(tert-butyl-dimethyl-silanyloxy)-cyclopent-2-enyl ester [synthesized by silylation of commercially available acetic acid (1S,4R)-4-hydroxy-cyclopent-2-enyl ester (Curran, et al. Tetrahedron 1997, 53, 1983-2004)] in 6 mL tetrahydrofuran with a solution of 320 mg (4.91 mmol) of sodium azide in 1.3 mL of water. To this biphasic mixture was added a solution of 112 mg (0.12 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 258 mg (0.98 mmol) of triphenylphosphine in 2 mL tetrahydrofuran, and the reaction mixture was heated to 50° C. for 6 h, when the reaction was complete. Sat. sodium chloride solution was added, and the aqueous phase was repeatedly extracted with ether. The combined organic phase was dried over sodium sulfate, filtered and evaporated. The crude material was purified by silica gel chromatography to yield 475 mg of the title compound (35). 1H NMR (400 MHz, DMSO) δ=0.09 (s, 3H), 0.10 (s, 3H), 0.88 (s, 9H), 1.49 (dt, J=3.9, 14.0 Hz, 1H), 2.69 (dt, J=7.4, 14.1 Hz, 1H), 4.22-4.26 (m, 1H), 4.75-4.79 (m, 1H), 5.92-5.95 (m, 1H), 6.05 (dt, J=1.8, 5.4 Hz, 1H)

後処理

  1. customThe title compound was prepared
  2. extractionthe aqueous phase was repeatedly extracted with ether
  3. dry with materialThe combined organic phase was dried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customThe crude material was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-a54799bee101414789cc10a2d67d3e39
出典データセット
uspto-grants-2014_06
特許番号
US08742116B2

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