Chlorotrimethylsilane → (5S,3R)-5-[(tert-Butyldiphenylsilyl)hydroxymethyl]-dihydro-3-(phenylselenenyl)-2(3H)-furanone

HRID 2213068Notes

Reaction equation

HRID 2213068 reaction equation
[Si:1]([CH:18]([OH:25])[C@H:19]1[O:23][C:22](=[O:24])[CH2:21][CH2:20]1)([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.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[Si](Cl)(C)(C)C.[C:41]1([Se:47]Br)[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1>C1COCC1.CCOCC>[Si:1]([CH:18]([OH:25])[C@H:19]1[O:23][C:22](=[O:24])[C@H:21]([Se:47][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[CH2:20]1)([C:14]([CH3:17])([CH3:15])[CH3:16])([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

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 123446BromoselenobenzeneHCID 2733832Lithium HexamethyldisilazideHCID 66739120HCID 66739120, compound

Product 1

HCID 87130933(5S,3R)-5-[(tert-Butyldiphenylsilyl)hydroxymethyl]-dihydro-3-(phenylselenenyl)-2(3H)-furanoneYield 58.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 4 (5 g, 14.1 mmol) in anhydrous THF (50 mL) at −78° C. was added lithium bis(trimethylsilyl)amide (1 M solution in THF, 15.8 mL, 15.8 mmol) over a period of 10 min. After stirring at −78° C. for 1 h, Me3SiCl (1.918 g, 17.65 mmol) was added dropwise, and the reaction mixture was allowed to warm to room temperature. After being stirred at room temperature for 30 min, the mixture was cooled to −78° C., and a solution of PhSeBr (5 g, 21.19 mmol) in anhydrous THF (25 mL) was added rapidly. The mixture was diluted with ether (50 mL), washed with water until the color of organic layer changed from dark brown to light yellow, dried (Na2SO4), filtered, and evaporated. The resulting oily residue [containing 3R(α, 5) and 3S(β) isomers; TLC: hexane/EtOAc, 10:1; Rf=0.42 and 0.28, respectively] was purified by flash chromatography on silica gel eluting with hexane/EtOAc (99:1 to 95:5) to give the title compound 5 as a light yellow oil (4.22 g, 59/%). 1H NMR (CDCl3) δ7.69–7.60 (m, 6H, arom.), 7.46–7.30 (m, 9H, arom.), 4.37–4,34 (m, 1H, H-5), 4.12–4.08 (m, 1H, H-3), 3.86–3.82 (dd, J=3 & 11 Hz, 1H, CH2OH), 3.62–3.59 (dd, J=3 & 11 Hz, 1H, CH2OH), 2.73–2.67 (m, 1H, H-4), 2.32–2.28 (m, 1H, H-4), 1.02 (s, 9H, t-Bu).

Workup

  1. temperatureto warm to room temperature
  2. stirringAfter being stirred at room temperature for 30 min
  3. temperaturethe mixture was cooled to −78° C.
  4. washwashed with water until the color of organic layer
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated
  8. additionThe resulting oily residue [containing 3R(α
  9. customRf=0.42 and 0.28, respectively] was purified by flash chromatography on silica gel eluting with hexane/EtOAc (99:1 to 95:5)

Sources & evidence

ORD record
ord-e2d0faa5a3c24f799205244c8cd4b16f
Source dataset
uspto-grants-2006_09
Patent number
US07105527B2

Reaction notes

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