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

HRID 1944096Notes

Reaction equation

HRID 1944096 reaction equation
[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

Participants

6

Reactant 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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

(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.

Workup

  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

Sources & evidence

ORD record
ord-55523a9ad97c4836ba3999c0ffd1d8bf
Source dataset
uspto-grants-2013_03
Patent number
US08394772B2

Reaction notes

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