CID 406 → 4-Chloro-3-methoxy-1-(methoxy-5-chloro-tricyclo[3,3,1,13,7]dec-2-ylidenemethyl)-benzene

HRID 357637Notes

Reaction equation

[CH3:1][O:2][CH:3]([C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[C:14]([O:19][CH3:20])[CH:13]=1)P(OCC)(=O)OCC.[Li]CCCC.P(=O)([O-])[O-].[Cl:30][C:31]12[CH2:40][CH:35]3[CH2:36][CH:37]([CH2:39][CH:33]([C:34]3=O)[CH2:32]1)[CH2:38]2>C1COCC1>[Cl:18][C:15]1[CH:16]=[CH:17][C:12]([C:3]([O:2][CH3:1])=[C:36]2[CH:37]3[CH2:39][CH:33]4[CH2:32][C:31]([Cl:30])([CH2:40][CH:35]2[CH2:34]4)[CH2:38]3)=[CH:13][C:14]=1[O:19][CH3:20]

Participants

Conditions

Temperature: -78 °C

Procedure

Phosphonate 4 (3.2 g, 10 mmol) was dissolved in 30 ml dry THF under argon and cooled to -78° C. Dropwise addition of nBuLi (2.3M, 4.4 ml, 10.1 mmol) generated a yellow-orange phosphonate ylid. After stirring the ylid solution for 10 min, 5-chloro-2 adamantanone (1.75 g, 9.5 mmol), dissolved in 8 ml THF, was added dropwise to the ylid at -78° C. The reaction was slowly warmed to room temperature over 45 min and refluxed for 2 h. Upon cooling, the THF was stripped in vacuo and the product was partitioned between EtOAc/hexanes (1:1) and dilute NaHCO3. The organic layer was dried over NaHCO3. The organic layer was dried over Na2SO4, stripped of solvent and purified on silica gel (2-4% EtOAc/hexanes) to give 3.3 g (96%) of enol ether 5 as a colorless, viscous gum.

Workup

additionwas added dropwise to the ylid at -78° C
temperatureThe reaction was slowly warmed to room temperature over 45 min
temperaturerefluxed for 2 h
temperatureUpon cooling
customthe product was partitioned between EtOAc/hexanes (1:1) and dilute NaHCO3
dry with materialThe organic layer was dried over NaHCO3
dry with materialThe organic layer was dried over Na2SO4
custompurified on silica gel (2-4% EtOAc/hexanes)

Sources & evidence

ORD record: ord-9817a0c4413b4970bcfd658d9971e3e3
Source dataset: uspto-grants-1998_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05840919

Reaction notes

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