Imidazole → tert-butyl(((5R,6S,6aS)-6-iodo-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-5-yl)methoxy)diphenylsilane

HRID 409007Notes

Reaction equation

HRID 409007 reaction equation
[Si:1]([O:18][CH2:19][C@H:20]1[O:27][CH:26]2[C@:22]([CH3:30])([O:23][C:24]([CH3:29])([CH3:28])[O:25]2)[C@@H:21]1O)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1C=CN=C1.[I:56]I>C1(C)C=CC=CC=1>[C:14]([Si:1]([O:18][CH2:19][C@H:20]1[O:27][CH:26]2[C@:22]([CH3:30])([O:23][C:24]([CH3:28])([CH3:29])[O:25]2)[C@H:21]1[I:56])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)([CH3:15])([CH3:16])[CH3:17]

Participants

6

Reactant 4

HCID 795ImidazoleHCID 807IodineHCID 11776TriphenylphosphineHCID 66780009(5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-ol

Product 1

HCID 66778990tert-butyl(((5R,6S,6aS)-6-iodo-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-5-yl)methoxy)diphenylsilaneYield 80%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a mixture of (5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-ol (from step 5) (32.4 g, 0.0736 mol), triphenylphosphine (57.9 g, 0.2209 mol), Imidazole (15.03 g, 0.2209 mol) in 400 mL anhydrous toluene was added iodine (42.96 g, 0.169 mol) in portions over a period of 30 min and refluxed for 12 h. The mixture was diluted with 300 mL toluene and washed with saturated NaHCO3 solution and saturated sodium thiosulfate solution. The organic layers were dried over anhydrous Na2SO4, filtered and concentrated. Purification was done by column chromatography using a gradient mixture of hexane and ethyl ether to give 32.08 g (80% yield) of the title compound.

Workup

  1. temperaturerefluxed for 12 h
  2. washwashed with saturated NaHCO3 solution and saturated sodium thiosulfate solution
  3. dry with materialThe organic layers were dried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification
  7. additiona gradient mixture of hexane and ethyl ether

Sources & evidence

ORD record
ord-f6a790c00e28444c8084220b385e351f
Source dataset
uspto-grants-2014_06
Patent number
US08759318B2

Reaction notes

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