Diiodomethane → HCID 66588531, compound

HRID 1092442Notes

Reaction equation

HRID 1092442 reaction equation
[CH2:1]([O:8][CH2:9][C@H:10]1[C:15](=[CH2:16])[C@@H:14]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]3[CH:30]=[CH:29][C:28]([CH2:31][CH3:32])=[CH:27][CH:26]=3)[CH:18]=2)[C@H:13]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C@@H:12]([O:41][CH2:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[C@@H:11]1[O:49][CH2:50][C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:57][Zn]C.ICI.[NH4+].[Cl-]>C1(C)C=CC=CC=1.O>[CH2:50]([O:49][C@H:11]1[C@H:12]([O:41][CH2:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[C@@H:13]([O:33][CH2:34][C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[C@H:14]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]3[CH:30]=[CH:29][C:28]([CH2:31][CH3:32])=[CH:27][CH:26]=3)[CH:18]=2)[C:15]2([CH2:57][CH2:16]2)[C@@H:10]1[CH2:9][O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:51]1[CH:52]=[CH:53][CH:54]=[CH:55][CH:56]=1

Participants

7

Reactant 4

HCID 6346Diiodomethane2×HCID 25517Ammonium ChlorideHCID 66588515HCID 66588515, compoundHCID 178477796HCID 178477796, compound2×

Product 1

HCID 66588531HCID 66588531, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a vigorously stirred solution of ((1S,2R,3R,4R,6S)-4-(benzyloxymethyl)-6-(4-chloro-3-(4-ethylbenzyl)phenyl)-5-methylenecyclohexane-1,2,3-triyl)tris(oxy)tris(methylene)-tribenzene (34, 25 mg, 32.7 μmol) in anhydrous toluene (2 mL) under nitrogen at −10° C. was added 2M solution of dimethyl zinc (146 μL, 291 μmol) dropwise and stirred for 15 minutes. Diiodomethane (47 μL, 583 μmol) was added drop-wise and the resulting mixture was stirred over night. 40% product fonnation was observed. More dimethyl zinc (18 more equivalent in two batches over 48 hour period) and diiodomethane (35 equivalent in two batches over 48 hour period) were added and the reaction was 80% complete after 96 hours of reaction. Saturated solution of NH4Cl (1 mL) was added and the mixture was stirred for 30 minutes. The mixture was diluted with water (1 mL) and extracted into ethyl acetate (3×1 mL). The combined organic extracts were washed with 10% sulfuric acid (1.5 mL), saturated NaHCO3 (1.5 mL) and brine (1.5 mL), dried (Na2SO4), filtered and evaporated. Preparative TLC (9:1 hexane:ethyl acetate) afforded 85% compound 36 which was used directly in the next reaction.

Workup

  1. stirringthe resulting mixture was stirred over night
  2. customcomplete after 96 hours
  3. customof reaction
  4. stirringthe mixture was stirred for 30 minutes
  5. extractionextracted into ethyl acetate (3×1 mL)
  6. washThe combined organic extracts were washed with 10% sulfuric acid (1.5 mL), saturated NaHCO3 (1.5 mL) and brine (1.5 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customevaporated

Sources & evidence

ORD record
ord-c5291d6ad8d44aa4838a900e7e0ed89f
Source dataset
uspto-grants-2012_03
Patent number
US08129434B2

Reaction notes

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