Trimethylsilyldiazomethane → [2-(3-Ethynyl-cyclohex-3-enyl)ethoxy]-triisopropyl-silane

HRID 2099426

Reaktionsgleichung

Reaktionsgleichung von HRID 2099426
[Si](C=[N+]=[N-])(C)(C)C.[Li][CH2:9][CH2:10][CH2:11][CH3:12].[CH:13]([Si:16]([CH:31]([CH3:33])[CH3:32])([CH:28]([CH3:30])[CH3:29])[O:17][CH2:18][CH2:19][CH:20]1CC(C=O)=[CH:23][CH2:22][CH2:21]1)([CH3:15])[CH3:14]>C1COCC1>[C:11]([C:10]1[CH2:9][CH:20]([CH2:19][CH2:18][O:17][Si:16]([CH:31]([CH3:32])[CH3:33])([CH:28]([CH3:30])[CH3:29])[CH:13]([CH3:14])[CH3:15])[CH2:21][CH2:22][CH:23]=1)#[CH:12]

Komponenten

5

Edukt 3

HCID 167693TrimethylsilyldiazomethaneHCID 219862035-(2-Triisopropylsilanyloxy-ethyl)-cyclohex-1-enecarbaldehydeHCID 178418339Butyllithium

Produkt 1

HCID 21986068[2-(3-Ethynyl-cyclohex-3-enyl)ethoxy]-triisopropyl-silane

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

A solution of TMS-diazomethane (4.61 mL, 9.22 mmol) in THF (60 mL) was reacted with n-BuLi (5.0 mL, 7.99 mmol) at −78 EC for 0.5 h. 5-(2-triisopropylsilanyloxy-ethyl)-cyclohex-1-enecarbaldehyde (Intermediate R13) was added via cannula. The mixture was reacted at −78 EC for 1 h and at 0 EC for 1 h. After work-up and chromatographic purification, [2-(3-ethynyl-cyclohex-3-enyl)-ethoxy]-triisopropyl-silane (Intermediate R14) was isolated, 1.44 g (77%). To Intermediate R14 in THF (70 mL) at 0 EC was injected tetrabutyl ammonium fluoride (TBAF). After 2 h at rt the mixture was subjected to an aqueous work-up. The material was purified by chromatography to give the alcohol, 2-(3-ethynyl-cyclohex-3-enyl)-ethanol 0.68 g, (98%). The alcohol was oxidized by a Swern reaction to the aldehyde stage and aldehyde was subjected to the applicable step of Method A to yield 4-(3-ethynyl-cyclohex-3-enylmethyl)-1H-imidazole (Intermediate R15).

Aufarbeitung

  1. customThe mixture was reacted at −78 EC for 1 h and at 0 EC for 1 h
  2. customAfter work-up and chromatographic purification

Quellen und Nachweise

ORD-Eintrag
ord-914475ba52234fe0a27067b1bca807f9
Quelldatensatz
uspto-grants-2009_08
Patentnummer
US07569584B2

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