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 422168ノート

反応式

HRID 422168 の反応式
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

参加物

6

反応物 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

生成物 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 acid収率 34.3%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 178478483HCID 178478483、化合物触媒HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
60 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-55a8882ac3d34ab5a65f1a463815a4ed
出典データセット
uspto-grants-2012_01
特許番号
US08101605B2

反応ノート

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