Pentane → (R)-2-Methyl-propane-2-sulfinic acid [(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-(6-propoxy-pyridin-3-yl)-ethyl]-amide

HRID 1908668Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1908668
C([Li])(C)(C)C.CCCCC.Br[C:12]1[CH:13]=[CH:14][C:15]([O:18][CH2:19][CH2:20][CH3:21])=[N:16][CH:17]=1.[C:22]([Si:26]([CH3:38])([CH3:37])[O:27][CH2:28][CH:29]=[N:30][S@@:31]([C:33]([CH3:36])([CH3:35])[CH3:34])=[O:32])([CH3:25])([CH3:24])[CH3:23]>C1COCC1>[C:22]([Si:26]([CH3:38])([CH3:37])[O:27][CH2:28][C@H:29]([NH:30][S@@:31]([C:33]([CH3:36])([CH3:35])[CH3:34])=[O:32])[C:12]1[CH:17]=[N:16][C:15]([O:18][CH2:19][CH2:20][CH3:21])=[CH:14][CH:13]=1)([CH3:25])([CH3:24])[CH3:23]

Komponenten

6

Edukt 4

HCID 8003PentaneHCID 233940055-Bromo-2-propoxypyridineHCID 86644143(R,E)-N-(2-((tert-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamideHCID 178418306HCID 178418306, Verbindung

Produkt 1

HCID 71201913(R)-2-Methyl-propane-2-sulfinic acid [(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-(6-propoxy-pyridin-3-yl)-ethyl]-amide

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

A 1.7 M solution of tert-butyllithium in pentane (15.2 mL, 25.8 mmol) was added drop wise to a stirring solution of 5-bromo-2-propoxypyridine IM3 (2.54 g, 11.8 mmol) dissolved in dry THF (29.4 mL) at −78° C. under Ar. The solution was subsequently stirred at this temperature for 30 min. A solution of (R)-2-methyl-propane-2-sulfinic acid [2-(tert-butyl-dimethyl-silanyloxy)ethylidene]-amide IM49 (3.26 g, 11.8 mmol) in dry THF (15 mL) was then added drop wise at −78° C. and the solution was stirred at this temperature for 30 min. The cooling bath was removed and the mixture was allowed to reach room temperature overnight. The mixture was quenched with saturated aqueous NH4Cl solution (75 mL) and EtOAc (150 mL). The phases were separated and the organic layer was washed with brine and then dried over MgSO4. Flash chromatography (silica, 10-100% EtOAc in heptanes) gave (R)-2-Methyl-propane-2-sulfinic acid [(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-(6-propoxy-pyridin-3-yl)-ethyl]amide, the fastest eluding isomer, as a clear oil (2.33 g, 48%) sufficiently pure for the next step. Diastereomeric excess >95% based on 1H NMR.

Aufarbeitung

  1. stirringthe solution was stirred at this temperature for 30 min
  2. customThe cooling bath was removed
  3. waitto reach room temperature overnight
  4. customThe mixture was quenched with saturated aqueous NH4Cl solution (75 mL) and EtOAc (150 mL)
  5. customThe phases were separated
  6. washthe organic layer was washed with brine
  7. dry with materialdried over MgSO4

Quellen und Nachweise

ORD-Eintrag
ord-94808fd7e5b54a3b9c44cffbe5724a86
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08598213B2

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