Diiodomethane → HCID 86728591, compound

HRID 1410309Notes

Reaction equation

HRID 1410309 reaction equation
ICI.[CH2:4]([Zn]CC)C.[C:9]([O:12][CH2:13][C@@H:14]1[C@@H:19]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@H:18]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@@H:17]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:16]([C:44]2[CH:49]=[C:48]([CH2:50][C:51]3[CH:56]=[CH:55][C:54]([O:57][CH2:58][CH3:59])=[CH:53][CH:52]=3)[C:47]([Cl:60])=[CH:46][C:45]=2[O:61][CH2:62]/[CH:63]=[CH:64]\[CH2:65][OH:66])[O:15]1)(=[O:11])[CH3:10]>ClCCl>[C:9]([O:12][CH2:13][C@@H:14]1[C@@H:19]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@H:18]([O:28][CH2:29][C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C@@H:17]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:16]([C:44]2[CH:49]=[C:48]([CH2:50][C:51]3[CH:56]=[CH:55][C:54]([O:57][CH2:58][CH3:59])=[CH:53][CH:52]=3)[C:47]([Cl:60])=[CH:46][C:45]=2[O:61][CH2:62][CH:63]2[CH2:4][CH:64]2[CH2:65][OH:66])[O:15]1)(=[O:11])[CH3:10]

Participants

5

Reactant 3

HCID 6346DiiodomethaneHCID 71117288HCID 71117288, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 86728591HCID 86728591, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of diiodomethane (0.66 mL, 8.09 mmol) in dichloromethane (10 mL) was added diethyl zinc (1.1M solution in toluene, 3.7 mL, 4.05 mmol) at 0° C. and stirred for 15 min. The reaction mixture was cooled to −78° C. and ((2R,3R,4R,5S,6S)-3,4,5-tris(benzyloxy)-6-(4-chloro-5-(4-ethoxybenzyl)-2-((Z)-4-hydroxybut-2-enyloxy)phenyl)tetrahydro-2H-pyran-2-yl)methyl acetate (46, 0.82 mg, 1.01 mmol) in dichloromethane (5 mL) was added dropwise to the reaction mixture, slowly warmed up to −20° C. for 3 h. The reaction mixture was quenched with saturated ammonium chloride, extracted with ethyl acetate, and dried over magnesium sulfate. The organic layer was filtered and evaporated in vacuo and the residue was purified on a Biotage® apparatus (silica gel, 5 to 40% ethyl tetrahydrofuran in hexanes gradient) to give the title compound (47, 835 mg, 1.01 mmol, 100%, diastereomer in about 1:2 ratio) as colorless oil.

Workup

  1. temperatureslowly warmed up to −20° C. for 3 h
  2. customThe reaction mixture was quenched with saturated ammonium chloride
  3. extractionextracted with ethyl acetate
  4. dry with materialdried over magnesium sulfate
  5. filtrationThe organic layer was filtered
  6. customevaporated in vacuo
  7. customthe residue was purified on a Biotage® apparatus (silica gel, 5 to 40% ethyl tetrahydrofuran in hexanes gradient)

Sources & evidence

ORD record
ord-7cc5dadc54ae4a898dc40798ea5405c6
Source dataset
uspto-grants-2014_12
Patent number
US08921412B2

Reaction notes

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