Triphenylphosphine → 6,7,8-Tris-benzyloxy-5-[2-(4-methoxy-benzyl)-phenoxy]-4-oxa-spiro[2.5]octane

HRID 1944096ノート

反応式

HRID 1944096 の反応式
[CH2:1]([O:8][C@@H:9]1[C@@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:15]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:12]2([CH2:14][CH2:13]2)[O:11][CH:10]1[OH:33])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:34][O:35][C:36]1[CH:49]=[CH:48][C:39]([CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=2O)=[CH:38][CH:37]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[CH2:1]([O:8][CH:9]1[CH:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:15]([O:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[C:12]2([CH2:14][CH2:13]2)[O:11][CH:10]1[O:33][C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][C:41]=1[CH2:40][C:39]1[CH:38]=[CH:37][C:36]([O:35][CH3:34])=[CH:49][CH:48]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 2584512-(4-Methoxybenzyl)phenolHCID 5363146Diisopropyl azodicarboxylateHCID 67074661(6R,7S,8S)-6,7,8-Tris-benzyloxy-4-oxaspiro[2.5]octan-5-ol

生成物 1

HCID 759517366,7,8-Tris-benzyloxy-5-[2-(4-methoxy-benzyl)-phenoxy]-4-oxa-spiro[2.5]octane

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

(6R,7S,8S)-6,7,8-Tris-benzyloxy-4-oxaspiro[2.5]octan-5-ol (prepared according to an analogous procedure as described in J. Org. Chem. 2002, 67, 3733; Helv. Chim, Acta 1990, 73, 1329; Tetrahedron Lett. 1998, 39, 2021) (220 mg, 0.49 mmol) 2-(4-methoxybenzyl)-phenol (105 mg, 0.49 mmol) and triphenyl phosphine (155 mg, 0.59 mmol) were mixed under argon atmosphere followed by the addition of dry THF. The contents were cooled to 0° C. and DIAD (0.12 ml, 0.59 mmol) was added drop wise. The reaction mixture was refluxed for 12 hours and quenched with 1N dil. HCl (2 mL) and extracted with ethyl acetate (10×3 mL). Organic layer was washed with brine, dried over Na2SO4, concentrated under reduced pressure to give the crude product which was purified by flash column chromatography using 1:4 (Ethyl acetate:Hexane) as eluent to yield 200 mg of 5R,6R,7S,8S)-6,7,8-tris-benzyloxy-5-[2-(4-methoxy-benzyl)-phenoxy]-4-oxa-spiro[2.5]octane.

後処理

  1. temperatureThe reaction mixture was refluxed for 12 hours
  2. customquenched with 1N dil. HCl (2 mL)
  3. extractionextracted with ethyl acetate (10×3 mL)
  4. washOrganic layer was washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customto give the crude product which
  8. customwas purified by flash column chromatography

出典と根拠

ORDレコード
ord-55523a9ad97c4836ba3999c0ffd1d8bf
出典データセット
uspto-grants-2013_03
特許番号
US08394772B2

反応ノート

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