Water → HCID 59516396, compound

HRID 1160589Notes

Reaction equation

HRID 1160589 reaction equation
[Si:1]([O:8][CH:9]1[CH2:20][C:19](=[O:21])[O:18][C@H:17](/[C:22](/[CH3:26])=[CH:23]/[CH:24]=O)[C@@H:16]([CH3:27])[CH:15]=[CH:14][C@@H:13]2[O:28][C@H:29]([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[O:30][C@:12]2([CH3:37])[CH2:11][CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].N1C=CC=C[CH:39]=1.O>C1COCC1.C1(C)C=CC=CC=1.C(OCC)(=O)C.[CH3-].C[Al+]C.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Cl-].[Ti+3]>[Si:1]([O:8][C@H:9]1[CH2:20][C:19](=[O:21])[O:18][C@H:17](/[C:22](/[CH3:26])=[CH:23]/[CH:24]=[CH2:39])[C@@H:16]([CH3:27])[CH:15]=[CH:14][C@@H:13]2[O:28][C@H:29]([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[O:30][C@:12]2([CH3:37])[CH2:11][CH2:10]1)([C:4]([CH3:6])([CH3:5])[CH3:7])([CH3:3])[CH3:2]

Participants

8

Reactant 3

HCID 962WaterHCID 1049PyridineHCID 59444759HCID 59444759, compound

Product 1

HCID 59516396HCID 59516396, compoundYield 76.6%

Reagents, catalysts & solvents 4

HCID 53384502mu-Chlorobis(eta5-cyclopentadienyl)(dimethylaluminum)-mu-methylenetitaniumCatalystHCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-40 °C

Procedure

(2S,3aS,4E,6S,7S,13aR)-11-{[tert-butyl(dimethyl)silyl]oxy}-7-[(E)-2-formyl-1-methyleth-1-en-1-yl]-6,13a-dimethyl-2-phenyl-3a,6,7,10,11,12,13,13a-octahydro-9H-[1,3]dioxolo[4,5-f]oxacyclododecin-9-one (50 mg, 0.09 mmol) was dissolved in a mixed solvent of THF (0.4 ml) and toluene (2.8 ml), and the solution was cooled to −40° C. After addition of pyridine (0.38 ml, 4.73 mmol) and 0.5M toluene solution (1.14 ml, 0.57 mmol) of Tebbe reagent (chlorobis(cyclopentadienyl)-(dimethylaluminum)-methylene titanium), the mixture was stirred at the same temperature for 30 minutes. It was warmed to room temperature and further stirred for one hour. Distilled water (1 ml) was added to the reaction solution, and the reaction solution was diluted with ethyl acetate and washed with distilled water and brine sequentially, and after dried over anhydrous sodium sulfate, the drying agent was filtered off and the organic layer was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (Merck, commercial name Silica Gel 60, 230-400 mesh; hexane:diethyl ether=4:1) to obtain the title compound (36.3 mg) as a colorless amorphous substance.

Workup

  1. temperatureIt was warmed to room temperature
  2. stirringfurther stirred for one hour
  3. washwashed with distilled water and brine sequentially
  4. dry with materialafter dried over anhydrous sodium sulfate
  5. filtrationthe drying agent was filtered off
  6. concentrationthe organic layer was concentrated under reduced pressure
  7. customThe obtained residue was purified by silica gel column chromatography (Merck, commercial name Silica Gel 60, 230-400 mesh; hexane:diethyl ether=4:1)

Sources & evidence

ORD record
ord-cde59da4233c41f5b5b5b1d6a7a42c6f
Source dataset
uspto-grants-2010_10
Patent number
US07816401B2

Reaction notes

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