Water → HCID 11260882, compound

HRID 348238Notes

Reaction equation

HRID 348238 reaction equation
[C:1]([O:4][C:5]([CH3:8])([CH3:7])[CH3:6])(=[O:3])[CH3:2].C([N-]C(C)C)(C)C.[Li+].[O:17]=[C:18]([C@H:24]([CH3:40])[C@@H:25]([O:31][C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:38])[Cl:37])=[O:33])[C@@H:26]([CH3:30])[CH2:27][CH:28]=[CH2:29])[C:19]([CH3:23])([CH3:22])[CH:20]=[O:21].O>CCOCC.C1COCC1>[O:17]=[C:18]([C@H:24]([CH3:40])[C@@H:25]([O:31][C:32]([O:34][CH2:35][C:36]([Cl:37])([Cl:38])[Cl:39])=[O:33])[C@@H:26]([CH3:30])[CH2:27][CH:28]=[CH2:29])[C:19]([CH3:23])([CH3:22])[C@@H:20]([OH:21])[CH2:2][C:1]([O:4][C:5]([CH3:8])([CH3:7])[CH3:6])=[O:3]

Participants

7

Reactant 4

HCID 962WaterHCID 10908tert-Butyl acetateHCID 2724682Lithium diisopropylamideHCID 11211787(4R,5S,6S)-3-oxo-5-(2,2,2-trichloroethoxycarbonyloxy)-2,2,4,6-tetramethyl-8-nonenal

Product 1

HCID 11260882HCID 11260882, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-30 °C

Procedure

Tert-butyl acetate (0.865 mL) is added to a solution of lithium diisopropylamide (7.52 mmol) in 30 mL of ether at −78° C., and the mixture is stirred for 1 hour. A solution of bis(1,2:5,6-di-O-isopropylidene-α-L-glucofuranos-3-O-yl)cyclopentadienyltitanium chloride (8.34 mmol) in 90 mL of ether is added dropwise over 40 minutes, and the reaction is stirred for an additional 30 minutes at −78° C., warmed to −30° C. and kept for 45 minutes, then recooled to −78° C. A solution of (4R,5S,6S)-3-oxo-5-(2,2,2-trichloroethoxycarbonyloxy)-2,2,4,6-tetramethyl-8-nonenal (2.57 g) in 15 mL of ether is added over 10 minutes and the reaction is continued for 2 hours before addition of 14 mL of 5 M water in THF. The mix is stirred for 1 hour then filtered through Celite. The filtrate is washed with sat. aq. NaCl, and the brine layer is back extracted with ether. The organic phases are combined, dried with Na2SO4, filtered, and evaporated. The product is purified by chromatography on SiO2 (7% ethyl acetate/hexanes).

Workup

  1. stirringthe reaction is stirred for an additional 30 minutes at −78° C.
  2. waitkept for 45 minutes
  3. customrecooled to −78° C
  4. stirringThe mix is stirred for 1 hour
  5. filtrationthen filtered through Celite
  6. washThe filtrate is washed with sat. aq. NaCl
  7. extractionthe brine layer is back extracted with ether
  8. dry with materialdried with Na2SO4
  9. filtrationfiltered
  10. customevaporated
  11. customThe product is purified by chromatography on SiO2 (7% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-0df460f33817494f8cd2f813998b99ee
Source dataset
uspto-grants-2007_02
Patent number
US07176235B2

Reaction notes

Loading…