Diiodomethane → HCID 86718971, compound

HRID 1842835Notes

Reaction equation

HRID 1842835 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[C@H:14]2[O:15][C:16]([CH3:19])([CH3:18])[O:17][C@H:13]2[C@@H:12]([OH:20])[C:11]1=[CH2:21])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:22]([Zn]CC)C.ICI>CCOCC>[Si:1]([O:8][CH2:9][C@H:10]1[C:11]2([CH2:22][CH2:21]2)[C@H:12]([OH:20])[C@@H:13]2[O:17][C:16]([CH3:19])([CH3:18])[O:15][C@H:14]12)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 6346DiiodomethaneHCID 86718972HCID 86718972, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 86718971HCID 86718971, compoundYield 96.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 12 (3 g, 9.5 mmol) in anhydrous ether (50 mL) was added diethyl zinc (1.0 M solution in hexane, 24.2 mL, 28.6 mmol) followed by diiodomethane (4.6 mL, 57.3 mmol) at 0° C. The reaction mixture was allowed to room temperature and was refluxed for 8 hr. The reaction mixture was cooled to 0° C. and quenched with saturated NH4Cl solution (20 mL) and extracted with ether (2×60 mL). The combined organic layers were washed with water (30 mL), brine (30 mL), dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography (5% EtOAc/hexane) to afford 13 (3.0 g, 93%) as an oil. [α]24D −86.03° (c 2.01, CHCl3); 1H NMR (500 MHz, CDCl3) δ 4.55 (m, 1H), 4.49 (m, 1H), 4.08 (m, 1H), 3.59 (dd, J=3.0 & 9.5 Hz), 3.50 (dd, J=4.5 & 10.5 Hz, 1H), 2.22 (d, J=10.5 Hz, D2O exchange OH, 1H), 1.57 (m, 1H), 1.44 (s, 3H), 1.31 (s, 3H), 0.84 (m, 10H), 0.43 (m, 1H), 0.32 (m, 1H), 0.24 (1H), −0.06 (s, 6H). 13C NMR (125 MHz, CDCl3) 159.01, 115.9, 115.4, 86.85, 84.85, 79.48, 71.63, 57.21, 32.13, 31.54, 30.33, 29.24 23.83, 7.14, 0.015; HR-MS Calcd. For (C17H32O4Si)+ 328.2070, found 328.2195.

Workup

  1. customwas allowed to room temperature
  2. temperaturewas refluxed for 8 hr
  3. customquenched with saturated NH4Cl solution (20 mL)
  4. extractionextracted with ether (2×60 mL)
  5. washThe combined organic layers were washed with water (30 mL), brine (30 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by column chromatography (5% EtOAc/hexane)

Sources & evidence

ORD record
ord-abb6a06c32444b0ca5949694d692e260
Source dataset
uspto-grants-2015_02
Patent number
US08946242B2

Reaction notes

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