Potassium Acetate → (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxylic acid

HRID 422168Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 422168
FC(F)(F)S(OC1[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]2[C:8]=1[C@@:9]1([CH3:30])[C@H:18]([CH2:19][S:20]2)[C@:17]2([CH3:27])[C@H:12]([C:13]([CH3:29])([CH3:28])[CH2:14][CH2:15][CH2:16]2)[CH2:11][CH2:10]1)(=O)=O.[CH3:33][C:34]([O-:36])=[O:35].[K+]>CS(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].C(Cl)Cl>[CH3:26][O:25][C:23]1[CH:22]=[C:21]2[C:8]([C@@:9]3([CH3:30])[C@H:18]([CH2:19][S:20]2)[C@:17]2([CH3:27])[C@H:12]([C:13]([CH3:29])([CH3:28])[CH2:14][CH2:15][CH2:16]2)[CH2:11][CH2:10]3)=[C:33]([C:34]([OH:36])=[O:35])[CH:24]=1

Komponenten

6

Edukt 2

HCID 517044Potassium AcetateHCID 53241983(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-yl trifluoromethanesulfonate

Produkt 1

HCID 58294803(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxylic acidAusbeute 34,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 178478483HCID 178478483, VerbindungKatalysatorHCID 679Dimethyl SulfoxideLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

A mixture of (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-yl trifluoromethanesulfonate (32) (1.5 g, 3.0 mmol), KOAc (1.1 g, 12 mmol), Pd(OAc)2 (0.3 g, 2 mmol), dppf:CH2Cl2 1:1 (0.97 g, 1.3 mmol) was prepared in DMSO (15 mL) and purged with N2. The reaction mixture was subjected to carbon monoxide via a balloon. The mixture was stirred at 60° C. for 18 h. The reaction was cooled to room temperature and quenched with water, acidified with 1 M HCl and extracted with EtOAc. The organic layer was concentrated to dryness. The crude product was purified by flash chromatography on silica gel (CH2Cl2/EtOAc, 1:1) to yield (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxylic acid (74) (0.40 g, 34%) as a brown solid.

Aufarbeitung

  1. custompurged with N2
  2. temperatureThe reaction was cooled to room temperature
  3. customquenched with water
  4. extractionextracted with EtOAc
  5. concentrationThe organic layer was concentrated to dryness
  6. customThe crude product was purified by flash chromatography on silica gel (CH2Cl2/EtOAc, 1:1)

Quellen und Nachweise

ORD-Eintrag
ord-55a8882ac3d34ab5a65f1a463815a4ed
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08101605B2

Notizen zur Reaktion

Wird geladen…