N-[(E)-3-methylbutan-2-ylideneamino]-2,4,6-tri(propan-2-yl)benzenesulfonamide → (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(4-methyl-3-methylene-2-oxopentyl)carbamate

HRID 627091Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 627091
[CH:1]([C:4]1[CH:9]=C(C(C)C)C=C(C(C)C)[C:5]=1S(N/N=C(/C(C)C)\C)(=O)=O)(C)[CH3:2].C([Li])CCC.[Si:31]([O:38][CH2:39][C@@H:40]([N:43]([CH2:51][C:52](N(OC)C)=[O:53])[C:44](=[O:50])[O:45][C:46]([CH3:49])([CH3:48])[CH3:47])[CH:41]=[CH2:42])([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32]>CCCCCC.CN(CCN(C)C)C>[Si:31]([O:38][CH2:39][C@@H:40]([N:43]([CH2:51][C:52](=[O:53])[C:1](=[CH2:2])[CH:4]([CH3:9])[CH3:5])[C:44](=[O:50])[O:45][C:46]([CH3:48])([CH3:49])[CH3:47])[CH:41]=[CH2:42])([C:34]([CH3:35])([CH3:36])[CH3:37])([CH3:32])[CH3:33]

Komponenten

6

Edukt 3

HCID 12563993N-[(E)-3-methylbutan-2-ylideneamino]-2,4,6-tri(propan-2-yl)benzenesulfonamide2×HCID 89855339(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)amino)-2-oxoethyl)carbamate2×HCID 178418339Butyllithium

Produkt 1

HCID 131735279(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(4-methyl-3-methylene-2-oxopentyl)carbamate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8037N,N,N',N'-TetramethylethylenediamineLösungsmittelHCID 8058HexaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a suspension of (E)-2,4,6-triisopropyl-N′-(3-methylbutan-2-ylidene)benzenesulfonohydrazide (Intermediate 33, 8 g, 21.82 mmol) in hexane (65 mL) and TMEDA (6.50 mL) at −78° C. was added dropwise n-butyllithium (1.6M in hexanes) (34.1 mL, 54.56 mmol). The reaction mixture turned orange and was stirred for 30 minutes at −78° C., then was warmed to 0° C. and bubbling started immediately. The suspension became a yellow solution. After ˜15 minutes the bubbling stopped and (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)-amino)-2-oxoethyl)carbamate (Intermediate 5, 4.39 g, 10.91 mmol) was added as a solution in hexane (2 mL). After ˜15 minutes LC/MS shows desired product and no remaining Weinreb amide starting material. The reaction mixture was quenched with saturated sodium bicarbonate and extracted with ether twice. The ether extracts were dried over magnesium sulfate, filtered and concentrated to afford a yellow oil. Silica gel chromatography (0%-10% ethyl acetate/hexanes) afforded the desired product (2.219 g, 49.4%) as a light yellow oil.

Aufarbeitung

  1. temperaturewas warmed to 0° C.
  2. custombubbling
  3. waitAfter ˜15 minutes the bubbling stopped
  4. waitAfter ˜15 minutes LC/MS shows

Quellen und Nachweise

ORD-Eintrag
ord-8be8cd70b3784a9d9f31083787d009c0
Quelldatensatz
uspto-grants-2016_04
Patentnummer
US09309245B2

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