Cesium carbonate → 4-(5,5-Dioxo-5H-5lambda6-dibenzothiophen-3-yl)-1,4-diazabicyclo[3.2.2]nonane

HRID 553051ノート

反応式

HRID 553051 の反応式
C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N:47]12[CH2:55][CH2:54][CH:51]([CH2:52][CH2:53]1)[NH:50][CH2:49][CH2:48]2.Br[C:57]1[CH:58]=[CH:59][C:60]2[C:64]3[CH:65]=[CH:66][C:67](Br)=[CH:68][C:63]=3[S:62](=[O:71])(=[O:70])[C:61]=2[CH:72]=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[O:70]=[S:62]1(=[O:71])[C:63]2[CH:68]=[CH:67][CH:66]=[CH:65][C:64]=2[C:60]2[CH:59]=[CH:58][C:57]([N:50]3[CH:51]4[CH2:54][CH2:55][N:47]([CH2:53][CH2:52]4)[CH2:48][CH2:49]3)=[CH:72][C:61]1=2

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 3984071,4-Diazabicyclo(3.2.2)nonaneHCID 634876Binap, (A+-)-HCID 40718983,7-Dibromo-dibenzothiophene 5,5-dioxide

生成物 1

HCID 573347164-(5,5-Dioxo-5H-5lambda6-dibenzothiophen-3-yl)-1,4-diazabicyclo[3.2.2]nonane収率 36.1%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒2 回

反応条件

温度
90 °C

実験手順

A catalyst solution was prepared by mixing tris(dibenzylideneacetone)dipalladium (Pd2(dba)3; 15 mg, 0.016 mmol; Alfa) and racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP; 21 mg, 0.033 mmol; Strem) in toluene (1 mL) and heating the mixture to 90° C. for 15 min. The solution was cooled, and then added to a mixture of 1,4-diazabicyclo[3.2.2]nonane (105 mg, 0.83 mmol; see J. Med. Chem. 1993, 36, 2311) and 3,7-dibromodibenzothiophene-5,5-dioxide (0.60 g, 1.60 mmol; see J. Med. Chem. 1978, 21, 1084), in toluene (3 mL). Cs2CO3 (1.04 g, 3.2 mmol; Aldrich) was then added, and the reaction mixture was flushed with nitrogen and heated to 80-85° C. overnight. After cooling to room temperature, the mixture was filtered through diatomaceous earth and purified by chromatography (35 g silica gel, 1-10% gradient of NH4OH-MeOH (1:10) in CH2Cl2) to afford the title compound (102 mg, 0.30 mmol, 36% yield): MS (DCI/NH3) m/z 341 (M+H)+.

後処理

  1. customA catalyst solution was prepared
  2. temperatureThe solution was cooled
  3. customthe reaction mixture was flushed with nitrogen
  4. temperatureheated to 80-85° C. overnight
  5. temperatureAfter cooling to room temperature
  6. filtrationthe mixture was filtered through diatomaceous earth
  7. custompurified by chromatography (35 g silica gel, 1-10% gradient of NH4OH-MeOH (1:10) in CH2Cl2)

出典と根拠

ORDレコード
ord-1e159aaa31a64a288e38991f7db4184b
出典データセット
uspto-grants-2011_05
特許番号
US07951791B2

反応ノート

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