Imidazole → Tert-butyl((3aR,4R,6aR)-5-iodo-2,2-dimethyl-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-yloxy)diphenylsilane

HRID 470179Notes

Reaction equation

HRID 470179 reaction equation
[I:1][C:2]1[C@H:3]([OH:12])[C@@H:4]2[O:8][C:7]([CH3:10])([CH3:9])[O:6][C@@H:5]2[CH:11]=1.N1C=CN=C1.[Si:18](Cl)([C:31]([CH3:34])([CH3:33])[CH3:32])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>CN(C=O)C.CCOC(C)=O>[C:31]([Si:18]([O:12][C@@H:3]1[C@H:4]2[C@H:5]([O:6][C:7]([CH3:9])([CH3:10])[O:8]2)[CH:11]=[C:2]1[I:1])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)([CH3:34])([CH3:32])[CH3:33]

Participants

6

Reactant 3

HCID 795ImidazoleHCID 94078tert-ButyldiphenylchlorosilaneHCID 67250445(3aS,4R,6aR)-5-iodo-2,2-dimethyl-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-ol

Product 1

HCID 67251766Tert-butyl((3aR,4R,6aR)-5-iodo-2,2-dimethyl-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-yloxy)diphenylsilane

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

3aS,4R,6aR)-5-iodo-2,2-dimethyl-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-ol (5-3) (1.5 g, 5.3 mmol, 1 equiv) was dissolved in DMF (6 mL) and imidazole (1.3 g, 18/4 mmol, 3.5 equiv) was added followed by TBDPS-Cl (3.0 mL, 11.6 mmol, 2.2 equiv). The resulting mixture was stirred at ambient temperature for 30 minutes. Upon disappearance of starting material, the mixture was diluted with 50 mL EtOAc and washed with water (2×50 mL). The organic layer was dried over MgSO4, filtered and concentrated. The crude residue was purified by flash chromatography (120 g SiO2, 0-20% EtOAc in hexanes) to yield tert-butyl((3aR,4R,6aR)-5-iodo-2,2-dimethyl-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-yloxy)diphenylsilane (5-4) as a colorless oil. 1H NMR (500 MHz, CDCl3): δ 7.82 (t, J=8 Hz, 4H); 7.34-7.44 (m, 6H); 6.33 (s, 1H); 4.61 (dd, J=5.5, 2.0 Hz, 1H); 4.46 (dd, J=5.5, 2.0 Hz, 1H); 3.91 (t, J=5.5 Hz, 1H); 1.40 (s, 3H); 1.21 (s, 3 II); 1.16 (s, 9H).

Workup

  1. washwashed with water (2×50 mL)
  2. dry with materialThe organic layer was dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude residue was purified by flash chromatography (120 g SiO2, 0-20% EtOAc in hexanes)

Sources & evidence

ORD record
ord-4a4c0aa31e824064812da65114a522fb
Source dataset
uspto-grants-2014_01
Patent number
US08629275B2

Reaction notes

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