Triphenylphosphine → HCID 71117288, compound

HRID 1410308Notes

Reaction equation

HRID 1410308 reaction equation
[C:1]([O:4][CH2:5][C@@H:6]1[C@@H:11]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C@H:10]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@@H:9]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@H:8]([C:36]2[CH:41]=[C:40]([CH2:42][C:43]3[CH:48]=[CH:47][C:46]([O:49][CH2:50][CH3:51])=[CH:45][CH:44]=3)[C:39]([Cl:52])=[CH:38][C:37]=2[OH:53])[O:7]1)(=[O:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:73](O)/[CH:74]=[CH:75]\[CH2:76][OH:77].N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[C:1]([O:4][CH2:5][C@@H:6]1[C@@H:11]([O:12][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[C@H:10]([O:20][CH2:21][C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[C@@H:9]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@H:8]([C:36]2[CH:41]=[C:40]([CH2:42][C:43]3[CH:48]=[CH:47][C:46]([O:49][CH2:50][CH3:51])=[CH:45][CH:44]=3)[C:39]([Cl:52])=[CH:38][C:37]=2[O:53][CH2:73]/[CH:74]=[CH:75]\[CH2:76][OH:77])[O:7]1)(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 6437902-Butene-1,4-diol, (2Z)-HCID 71117342HCID 71117342, compound

Product 1

HCID 71117288HCID 71117288, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of ((2R,3R,4R,5S,6S)-3,4,5-tris(benzyloxy)-6-(4-chloro-5-(4-ethoxybenzyl)-2-hydroxyphenyl)tetrahydro-2H-pyran-2-yl)methyl acetate (45, 2.19 g, 2.97 mmol) from Step 1 in tetrahydrofuran (30 mL) were added triphenylphosphine (1.57 g, 5.94 mmol) and cis-2-butene-1,4-diol (0.5 mL, 5.94 mmol) at 0° C., and diisopropyl azodicarboxylate (1.35 mL, 6.53 mmol) was added dropwise thereto. The reaction mixture was stirred at ambient temperature for 0.5 h and warmed up to room temperature for 4 h. After cooling to 0° C., the reaction mixture was quenched with H2O, extracted with ethyl acetate and dried over magnesium sulfate. The crude residue was purified on Biotage® purification apparatus (silica gel, 10 to 45% tetrahydrofuran in hexanes) to yield the title compound (46, 2.08 g, 2.57 mmol, 87%) as colorless oil.

Workup

  1. temperaturewarmed up to room temperature for 4 h
  2. temperatureAfter cooling to 0° C.
  3. customthe reaction mixture was quenched with H2O
  4. extractionextracted with ethyl acetate
  5. dry with materialdried over magnesium sulfate
  6. customThe crude residue was purified on Biotage® purification apparatus (silica gel, 10 to 45% tetrahydrofuran in hexanes)

Sources & evidence

ORD record
ord-13a8dc6806f440cfbeae17ec7eb3ea31
Source dataset
uspto-grants-2014_12
Patent number
US08921412B2

Reaction notes

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